CN103597005B - Macromolecular compound and use its electronic component - Google Patents

Macromolecular compound and use its electronic component Download PDF

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CN103597005B
CN103597005B CN201280027740.3A CN201280027740A CN103597005B CN 103597005 B CN103597005 B CN 103597005B CN 201280027740 A CN201280027740 A CN 201280027740A CN 103597005 B CN103597005 B CN 103597005B
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CN103597005A (en
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大家健一郎
吉村研
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Sumitomo Chemical Co Ltd
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Abstract

Macromolecular compound containing the structural unit shown in formula (1), formula (2), formula (3) or formula (4) can be used in manufacturing the high organic thin film solar cell of opening end voltage.In following formula (1) ~ formula (4), Ar 1represent the aromatic carbon ring base of 3 valencys or the aromatic heterocycle of 3 valencys, Ar 2represent the aromatic carbon ring base of 4 valencys or the aromatic heterocycle of 4 valencys, Z represent-O-,-S-,-C (=O)-,-S (=O)-,-SO 2-,-Si (R) 2-,-N (R)-,-B (R)-,-P (R)-or-P (=O) (R)-, R represents the group of hydrogen atom, halogen atom or 1 valency.

Description

Macromolecular compound and use its electronic component
Technical field
The present invention relates to the macromolecular compound with ad hoc structure and the electronic component using it.
Background technology
In recent years, in order to prevent greenhouse effects of the earth, seek the CO released in air 2minimizing.Therefore, the sun power system (solar system) adopting and employ a kind of electronic component, i.e. pn junction silicon system solar cell is advocated.But, need high temperature and vacuum process in the mill as the silicon single crystal of the material of silicon system solar cell, polysilicon and non-crystalline silicon.
On the other hand, the organic thin film solar cell of the organic layer containing pbz polymer compound got most of the attention in recent years, it can omit the high-temperature process and high vacuum operation that use in the manufacturing process of silicon system solar cell, can manufacture at an easy rate by means of only painting process.As the macromolecular compound be used in organic thin film solar cell, propose the macromolecular compound (WO2007/011739) comprising repeating unit (A) and repeating unit (B).
But the organic thin film solar cell containing the organic layer containing this macromolecular compound, its opening end voltage is not necessarily enough high.
The invention provides a kind of macromolecular compound that can manufacture the fully high organic thin film solar cell of opening end voltage.
Summary of the invention
The present invention is as described below.
1. a macromolecular compound, it contains formula (1), formula (2), formula (3) or the structural unit shown in formula (4).
(in formula (1) ~ formula (4), Ar 1represent the aromatic carbon ring base of 3 valencys or the aromatic heterocycle of 3 valencys, Ar 2represent the aromatic carbon ring base of 4 valencys or the aromatic heterocycle of 4 valencys, Z represent-O-,-S-,-C (=O)-,-S (=O)-,-SO 2-,-Si (R) 2-,-N (R)-,-B (R)-,-P (R)-or-P (=O) (R)-, R represents the group of hydrogen atom, halogen atom or 1 valency, 2 Ar 1can be identical or different, 2 Z can be identical or different, and multiple R can be identical or different respectively.)〕
2. according to above-mentioned 1. macromolecular compound, wherein,
Formula (1), formula (2), formula (3) or the structural unit shown in formula (4) are formula (5), the structural unit shown in formula (6), formula (7) or formula (8),
(in formula (5) ~ formula (8), X represent sulphur atom, Sauerstoffatom, selenium atom ,-NH-or-N (R)-, Ar 2, Z and R represent implication same as described above, Y represents nitrogen-atoms or=CH-, and 2 X can be identical or different, and 2 Y can be identical or different.〕
3. according to above-mentioned 1. macromolecular compound, wherein,
Formula (1), formula (2), formula (3) or the structural unit shown in formula (4) are formula (9), the structural unit shown in formula (10), formula (11) or formula (12),
(in formula (9) ~ formula (12), Ar 2and R represents implication same as described above.〕
4. according to above-mentioned 1. ~ 3. macromolecular compound, wherein,
The number-average molecular weight of polystyrene conversion is more than 3000.
5. a film, it contains the macromolecular compound of above-mentioned 1. ~ 4..
6. a composition, it contains macromolecular compound and the electron acceptor compound of above-mentioned 1. ~ 4..
7. according to above-mentioned 6. composition, wherein, electron acceptor compound is fullerene derivate.
8. a film, it contains the composition of above-mentioned 6. or 7..
9. an electronic component, it uses the film of above-mentioned 5. or 8..
10. the compound shown in formula (13),
(in formula, R represents the group of hydrogen atom, halogen atom or 1 valency, and W represents hydrogen atom, halogen atom, boric acid ester residue, dihydroxyl boryl, formyl radical, vinyl or replaces stannyl, and 4 R can be identical or different respectively, and 2 W can be identical or different.〕
Compound shown in 11. 1 kinds of formulas (14),
(in formula, R represents the group of hydrogen atom, halogen atom or 1 valency, and W represents hydrogen atom, halogen atom, boric acid ester residue, dihydroxyl boryl, formyl radical, vinyl or replaces stannyl, and 4 R can be identical or different respectively, and 2 W can be identical or different.〕
Embodiment
Below, the present invention is explained.
Macromolecular compound of the present invention contains formula (1), formula (2), formula (3) or the structural unit shown in formula (4).
In formula (1) ~ formula (4), Z represent-O-,-S-,-C (=O)-,-S (=O)-,-SO 2-,-Si (R) 2-,-N (R)-,-B (R)-,-P (R)-or-P (=O) (R)-.From the view point of the easness of monomer of raw material creating macromolecular compound of the present invention, Z is-O-,-S-, more preferably-O-preferably.
In formula (1) ~ formula (4), R represents the group of hydrogen atom, halogen atom (fluorine atom, chlorine atom, bromine atoms and atomic iodine) or 1 valency.As the group of 1 valency, such as commutable alkyl can be enumerated, commutable alkoxyl group, commutable alkylthio, commutable aryl, commutable aryloxy, commutable arylthio, commutable aralkyl, commutable alkoxy aryl, commutable alkylthio-aryl, commutable acyl group, commutable acyloxy, amide group, imide, amino, substituted-amino, replace silyl, replace siloxy-, replace silyl sulfenyl, replace silyl amino, heterocyclic radical, heterocyclic oxy group, heterocyclethio, arylalkenyl, sweet-smelling alkynyl, carboxyl, cyano group.Multiple R can be identical or different.
Alkyl can be straight-chain, also can be branched, also can be ring-type.As the carbonatoms of alkyl, be generally 1 ~ 30.As the substituting group that alkyl can have, such as halogen atom can be enumerated.As the concrete example of alkyl, the chain-like alkyls such as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, isopentyl, 2-methyl butyl, 1-methyl butyl, hexyl, isohexyl, 3-methyl amyl, 2-methyl amyl, 1-methyl amyl, heptyl, octyl group, iso-octyl, 2-ethylhexyl, 3,7-dimethyl octyl groups, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl can be enumerated; The cycloalkyl such as cyclopentyl, cyclohexyl, adamantyl.
The alkyl portion of alkoxyl group can be straight-chain, also can be branched, also can be ring-type.As the substituting group that alkoxyl group can have, such as halogen atom can be enumerated.The carbonatoms of alkoxyl group is generally 1 ~ 20.As the concrete example can with substituent alkoxyl group, can enumerate methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, isobutoxy, tert.-butoxy, pentyloxy, hexyloxy, cyclohexyloxy, heptan oxygen base, octyloxy, 2-ethyl hexyl oxy, the ninth of the ten Heavenly Stems oxygen base, the last of the ten Heavenly stems oxygen base, 3,7-dimethyl octyloxies, lauryl oxygen base, trifluoromethoxy, five fluorine oxyethyl groups, perfluor butoxy, perfluor hexyloxy, perfluor octyloxy, methoxymethoxy and 2-methoxy ethoxy.
The alkyl portion of alkylthio can be straight-chain, also can be branched, also can be ring-type.As the substituting group that alkylthio can have, such as halogen atom can be enumerated.The carbonatoms of alkylthio is generally 1 ~ 20.As the concrete example can with substituent alkylthio, methylsulfany, ethylsulfanyl, propyl group sulfenyl, isopropylsulfanyl, butyl sulfenyl, i-butylthio, tert. butyl-sulphenyl, pentylthio, hexyl sulfenyl, cyclohexylthio, heptyl sulfenyl, octylthio, 2-ethylhexyl sulfenyl, nonyl sulfenyl, decyltliio, 3,7-dimethyl octylthio, lauryl sulfenyl and trifluoromethylsulfanyl can be enumerated.
Aryl refers to remaining atomic group after an aromatic nucleus removing hydrogen atom of aromatic hydrocarbon, and carbonatoms is generally 6 ~ 60.As the substituting group that aryl can have, such as halogen atom, commutable alkyl, commutable alkoxyl group, commutable alkylthio can be enumerated.The definition of commutable alkyl, commutable alkoxyl group and commutable alkylthio and concrete example thereof are identical with the definition of the commutable alkyl shown in R, commutable alkoxyl group and commutable alkylthio and concrete example thereof.As the concrete example of commutable aryl, phenyl can be enumerated, (C1 ~ C12 alkyl can illustrate the alkyl of carbonatoms 1 ~ 12 to C1 ~ C12 alkoxyl phenyl; Preferred C1 ~ C8 the alkyl of C1 ~ C12 alkyl, more preferably C1 ~ C6 alkyl; C1 ~ C8 alkyl represents the alkyl of carbonatoms 1 ~ 8, and C1 ~ C6 alkyl represents the alkyl of carbonatoms 1 ~ 6; As the concrete example of C1 ~ C12 alkyl, C1 ~ C8 alkyl and C1 ~ C6 alkyl, explanation, illustrative group in abovementioned alkyl can be enumerated; As follows), C1 ~ C12 alkyl phenyl, 1-naphthyl, 2-naphthyl and pentafluorophenyl group.
The carbonatoms of aryloxy is generally 6 ~ 60.As the substituting group that aryloxy can have, such as halogen atom, commutable alkyl, commutable alkoxyl group, commutable alkylthio can be enumerated.Definition and the concrete example of the definition of commutable alkyl, commutable alkoxyl group and commutable alkylthio and the commutable alkyl shown in concrete example with R, commutable alkoxyl group and commutable alkylthio are identical.As the concrete example of commutable aryloxy, phenoxy group, C1 ~ C12 alkoxyl group phenoxy group, C1 ~ C12 alkyl phenoxy, 1-naphthyl oxygen base, 2-naphthyl oxygen base and penta fluoro benzene oxygen base can be enumerated.
The carbonatoms of arylthio is generally 6 ~ 60.As the substituting group that arylthio can have, such as halogen atom, commutable alkyl, commutable alkoxyl group, commutable alkylthio can be enumerated.Definition and the concrete example of the definition of commutable alkyl, commutable alkoxyl group and commutable alkylthio and the commutable alkyl shown in concrete example with R, commutable alkoxyl group and commutable alkylthio are identical.As the concrete example of commutable arylthio, phenylsulfartyl, C1 ~ C12 alkoxyl phenyl sulfenyl, C1 ~ C12 alkyl phenyl sulfenyl, 1-naphthylthio, 2-naphthylthio and pentafluorophenyl group sulfenyl can be enumerated.
The carbonatoms of aralkyl is generally 7 ~ 60.As the substituting group that aralkyl can have, such as halogen atom, commutable alkyl, commutable alkoxyl group, commutable alkylthio can be enumerated.Definition and the concrete example of the definition of commutable alkyl, commutable alkoxyl group and commutable alkylthio and the commutable alkyl shown in concrete example with R, commutable alkoxyl group and commutable alkylthio are identical.In addition, moieties can have the substituting groups such as halogen atom.As the concrete example can with substituent aralkyl, phenyl-C1 ~ C12 alkyl, C1 ~ C12 alkoxyl phenyl-C1 ~ C12 alkyl, C1 ~ C12 alkyl phenyl-C1 ~ C12 alkyl, 1-naphthyl-C1 ~ C12 alkyl and 2-naphthyl-C1 ~ C12 alkyl can be enumerated.
The carbonatoms of alkoxy aryl is generally 7 ~ 60.As the substituting group that alkoxy aryl can have, such as halogen atom, commutable alkyl, commutable alkoxyl group, commutable alkylthio can be enumerated.Definition and the concrete example of the definition of commutable alkyl, commutable alkoxyl group and commutable alkylthio and the commutable alkyl shown in concrete example with R, commutable alkoxyl group and commutable alkylthio are identical.In addition, alkoxy portion can have the substituting groups such as halogen atom.As the concrete example can with substituent alkoxy aryl, phenyl-C1 ~ C12 alkoxyl group, C1 ~ C12 alkoxyl phenyl-C1 ~ C12 alkoxyl group, C1 ~ C12 alkyl phenyl-C1 ~ C12 alkoxyl group, 1-naphthyl-C1 ~ C12 alkoxyl group and 2-naphthyl-C1 ~ C12 alkoxyl group can be enumerated.
The carbonatoms of alkylthio-aryl is generally 7 ~ 60.As the substituting group that alkylthio-aryl can have, such as halogen atom, commutable alkyl, commutable alkoxyl group, commutable alkylthio can be enumerated.Definition and the concrete example of the definition of commutable alkyl, commutable alkoxyl group and commutable alkylthio and the commutable alkyl shown in concrete example with R, commutable alkoxyl group and commutable alkylthio are identical.In addition, alkylthio moieties can have the substituting groups such as halogen atom.As the concrete example can with substituent alkylthio-aryl, phenyl-C1 ~ C12 alkylthio, C1 ~ C12 alkoxyl phenyl-C1 ~ C12 alkylthio, C1 ~ C12 alkyl phenyl-C1 ~ C12 alkylthio, 1-naphthyl-C1 ~ C12 alkylthio and 2-naphthyl-C1 ~ C12 alkylthio can be enumerated.
Acyl group is generally the alkyl carbonyl that carbonatoms is 2 ~ 20.As the substituting group that acyl group can have, such as halogen atom can be enumerated.As the concrete example can with substituent acyl group, ethanoyl, propionyl, butyryl radicals, isobutyryl, pivaloyl group, benzoyl, trifluoroacetyl group and pentafluorobenzoyl can be enumerated.
The carbonatoms of acyloxy is generally 2 ~ 20.As the substituting group that acyloxy can have, such as halogen atom can be enumerated.As the concrete example can with substituent acyloxy, acetoxyl group, propionyloxy, butyryl acyloxy, isobutyl acyloxy, pivaloyl oxygen base, benzoyloxy, trifluoroacetyl oxygen base and penta fluoro benzene methanoyl can be enumerated.
As amide group, representational is commutable alkyl carbonylamino, and its carbonatoms is generally 1 ~ 20.Alternatively base, can enumerate such as halogen atom.As the concrete example of amide group, formamido-, acetamido, propionamido-, amide-based small, benzoylamino, trifluoroacetyl amido and penta fluoro benzene formamido-can be enumerated.
As imide, representational have diacylamino group, and this acyl group portion can have substituting group.Alternatively base, can enumerate such as halogen atom.As the concrete example of imide, succinimido, phthalimide-based, diformamide base, diacetyl amino can be enumerated, two propanoylamino, dibutyryl are amino, amino, the two trifluoroacetyl group of dibenzoyl is amino and two pentafluorobenzoyl is amino.
The carbonatoms of substituted-amino is generally 1 ~ 40.Alternatively the amino substituting group had, can enumerate such as commutable alkyl and aryl.Definition and the concrete example of the definition of commutable alkyl and aryl and the commutable alkyl shown in concrete example with R and aryl are identical.Alternatively amino concrete example, can enumerate methylamino, dimethylamino, ethylamino, diethylamino, propylcarbamic, dipropylamino, isopropylamino, diisopropylaminoethyl, butyl is amino, isobutylamino, tert-butylamino, pentyl amino, hexylamino, Cyclohexylamino, heptyl is amino, octyl amino, 2-ethylhexylamino, nonylamino, Decylamino, 3,7-dimethyl octyl amino, lauryl amino, clopentylamino, bicyclopentyl is amino, Cyclohexylamino, dicyclohexyl is amino, pyrrolidyl, piperidyl, two (trifluoromethyl) is amino, phenyl amino, diphenyl amino, C1 ~ C12 alkoxyl phenyl is amino, two (C1 ~ C12 alkoxyl phenyl) is amino, two (C1 ~ C12 alkyl phenyl) is amino, 1-naphthyl-amino, 2-naphthyl-amino, pentafluorophenyl group is amino, pyridinylamino, pyridazinyl is amino, pyrimidinyl-amino, pyrazinyl is amino, triazine radical amido, phenyl-C1 ~ C12 alkylamino, C1 ~ C12 alkoxyl phenyl-C1 ~ C12 alkylamino, C1 ~ C12 alkyl phenyl-C1 ~ C12 alkylamino, two (C1 ~ C12 alkoxyl phenyl-C1 ~ C12 alkyl) is amino, two (C1 ~ C12 alkyl phenyl-C1 ~ C12 alkyl) is amino, 1-naphthyl-C1 ~ C12 alkylamino and 2-naphthyl-C1 ~ C12 alkylamino.
Alternatively the substituting group that has of silyl, can enumerate such as commutable alkyl and aryl.Definition and the concrete example of the definition of commutable alkyl and aryl and the commutable alkyl shown in concrete example with R and aryl are identical.The alternatively concrete example of silyl, can enumerate trimethyl silyl, triethylsilyl, tripropylsilyl base, triisopropyl silyl, t-butyldimethylsilyl, triphenyl-silyl, three (p-Xylol base) silyl, tribenzyl silyl, diphenylmethylsilyl, t-butyldiphenylsilyl and dimethylphenylsilyl.
Alternatively the substituting group that has of siloxy-, can enumerate such as commutable alkyl and aryl.Definition and the concrete example of the definition of commutable alkyl and aryl and the commutable alkyl shown in concrete example with R and aryl are identical.The alternatively concrete example of siloxy-, can enumerate trimethylsiloxy, silicoheptane alcoxyl base, tripropylsilyl oxygen base, triisopropyl siloxy-, t-butyldimethylsilyloxy base, triphenylsiloxy group, three (p-Xylol base) siloxy-, tribenzyl siloxy-, diphenyl methyl siloxy-, t-butyidiphenylsilyl oxygen base and dimethylphenylsilane oxygen base.
Alternatively the substituting group that has of silyl sulfenyl, can enumerate such as commutable alkyl and aryl.Definition and the concrete example of the definition of commutable alkyl and aryl and the commutable alkyl shown in concrete example with R and aryl are identical.The alternatively concrete example of silyl sulfenyl, can enumerate trimethyl silyl sulfenyl, silicoheptane alkylthio, tripropylsilyl sulfenyl, triisopropyl silylthio-, t-butyl-dimethylsilyl sulfenyl, triphenylsilyl sulfenyl, three (p-Xylol base) silylthio-, tribenzyl silylthio-, diphenyl methyl silylthio-, t-butyidiphenylsilyl sulfenyl and dimethylphenylsilane sulfenyl.
Alternatively the amino substituting group had of silyl, can enumerate such as commutable alkyl and aryl.Definition and the concrete example of the definition of commutable alkyl and aryl and the commutable alkyl shown in concrete example with R and aryl are identical.The alternatively concrete example of silyl amino, can enumerate trimethyl silyl amino, triethylsilyl is amino, tripropylsilyl base is amino, triisopropyl silyl is amino, t-butyldimethylsilyl is amino, triphenyl-silyl is amino, three (p-Xylol base) silyl is amino, tribenzyl silyl is amino, diphenylmethylsilyl is amino, t-butyldiphenylsilyl is amino, dimethylphenylsilyl is amino, two (trimethyl silyl) is amino, two (triethylsilyl) is amino, two (tripropylsilyl base) is amino, two (triisopropyl silyl) is amino, two (t-butyldimethylsilyl) is amino, two (triphenyl-silyl) is amino, two (three (p-Xylol base) silyl) is amino, two (tribenzyl silyl) is amino, two (diphenylmethylsilyl) is amino, two (t-butyldiphenylsilyl) is amino, two (dimethylphenylsilyl) is amino.
Heterocyclic radical refers to remaining atomic group after the hydrogen atom that can have substituent heterogeneous ring compound on removing 1 heterocycle.As heterogeneous ring compound, such as furans can be enumerated, thiophene, pyrroles, pyrroline, tetramethyleneimine, oxazole, isoxazole, thiazole, isothiazole, imidazoles, tetrahydroglyoxaline, imidazolidine (imidazolidine), pyrazoles, pyrazoline, pyrazolidine, furazan (furazan), triazole, thiadiazoles, oxadiazole, tetrazolium, pyrans, pyridine, piperidines, thiapyran, pyridazine, pyrimidine, pyrazine, piperazine, morpholine, triazine, cumarone, isobenzofuran, thionaphthene, indoles, isoindole, indolizine, indoline, isoindoline, chromene, chroman (chroman), heterochromatic full, chromene, quinoline, isoquinoline 99.9, quinolizine, benzoglyoxaline, benzothiazole, indazole, naphthyridines (naphthyridine), quinoxaline, quinazoline, quinoline azoles alkane (quinazolidine), cinnolines, phthalazines, purine, pteridine (pteridin), carbazole, xanthene, phenanthridines, acridine, β-carboline, perimidine (perimidine), phenanthroline, thianthrene, phenoxathiin (phenoxathiin), phenoxazine, thiodiphenylamine and azophenlyene.As the substituting group that heterogeneous ring compound can have, such as halogen atom, commutable alkyl, commutable alkoxyl group and commutable alkylthio can be enumerated.Definition and the concrete example of the definition of commutable alkyl, commutable alkoxyl group and commutable alkylthio and the commutable alkyl shown in concrete example with R, commutable alkoxyl group and commutable alkylthio are identical.As heterocyclic radical, optimization aromatic heterocyclic radical.
As heterocyclic oxy group, the group of bonding shown in the formula of Sauerstoffatom (A-1) can be enumerated on described heterocyclic radical.
As heterocyclethio, the group of bonding shown in the formula of sulphur atom (A-2) can be enumerated on described heterocyclic radical.
(in formula (A-1) and formula (A-2), Ar 3represent heterocyclic radical.)
As the concrete example of heterocyclic oxy group, thienyl oxygen base, C1 ~ C12 alkylthrophene base oxygen base, pyrryl oxygen base, furyl oxygen base, pyridyl oxygen base, C1 ~ C12 Alkylpyridyl oxygen base, imidazolyl oxygen base, pyrazoloxy, triazolyl oxygen Ji, oxazolyl oxygen base, thiazolyl oxygen base and thiazoldiazolioxo can be enumerated.
As the concrete example of heterocyclethio, thienyl sulfydryl, C1 ~ C12 alkylthrophene base sulfydryl, pyrryl sulfydryl, furyl sulfydryl, pyridyl sulfydryl, C1 ~ C12 Alkylpyridyl sulfydryl, imidazolyl sulfydryl, pyrazolyl sulfydryl, triazolyl sulfydryl, oxazolyl sulfydryl, thiazolyl sulfydryl and thiadiazolyl group sulfydryl can be enumerated.
Arylalkenyl usually its carbonatoms is 8 ~ 20.As the concrete example of arylalkenyl, styryl can be enumerated.
Sweet-smelling alkynyl usually its carbonatoms is 8 ~ 20.As the concrete example of sweet-smelling alkynyl, phenylene-ethynylene can be taken out.
From improving the deliquescent viewpoint of macromolecular compound of the present invention relative to solvent; the alkylthio of the alkyl of the preferred carbonatoms more than 6 of R, the alkoxyl group of carbonatoms more than 6, carbonatoms more than 6, aryl, aryloxy, arylthio, aralkyl, alkoxy aryl, alkylthio-aryl, the acyl group of carbonatoms more than 6 and the acyloxy of carbonatoms more than 6; be more preferably the alkyl of carbonatoms more than 6, the alkoxyl group of carbonatoms more than 6, aryl and aryloxy, the particularly preferably alkyl of carbonatoms more than 6.
As one of the optimal way i.e. alkyl of carbonatoms more than 6 of R, hexyl can be enumerated, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, tritriacontyl, tetratriacontane base, the alkyl of the straight-chain such as pentatriacontane base, 1, 1, 3, 3-tetramethyl butyl, 1-methylheptyl, 2-ethylhexyl, 3, 7-dimethyl octyl group, 1-propylpentyl, 2-hexyl decyl, 2-heptylundecanoic base, 2-octyldodecyl, 3, 7, 11-trimethyldodecane base, 3, 7, 11, 15-tetramethyl-hexadecyl, 3, 5, the alkyl of the branched such as 5-trimethyl.
The alkyl of carbonatoms more than 6 can consider that macromolecular compound of the present invention is suitably selected relative to the solvability etc. of solvent, preferred hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, 2-ethylhexyl, 3, 7-dimethyl octyl group, 1-propylpentyl and 2-hexyl decyl, more preferably hexyl, heptyl, octyl group, dodecyl, tetradecyl, hexadecyl, 2-ethylhexyl, 3, 7-dimethyl octyl group and 2-hexyl decyl, particularly preferably hexyl, octyl group, hexadecyl, 2-ethylhexyl and 3, 7-dimethyl octyl group.
As one of the preferred implementation i.e. commutable aryl of R, can suitably select relative to the solvability etc. of solvent by macromolecular compound according to the present invention, preferably by phenyl that alkyl replaces.The preferred contraposition of the position of substitution of alkyl.As the phenyl of alkyl at para-orientation, preferably to hexyl phenyl, to heptyl phenyl, to octyl phenyl, to nonyl phenyl, to decyl phenyl, to undecyl phenyl, to dodecylphenyl, to tridecyl phenyl, to tetradecyl phenyl, to pentadecylphenyl, to hexadecyl phenyl, to 2-ethylhexyl phenyl, to 3, 7-dimethyl octyl phenyl, to 1-propylpentyl phenyl and to 2-hexyl decyl phenyl, more preferably to hexyl phenyl, to heptyl phenyl, to octyl phenyl, to dodecylphenyl, to pentadecylphenyl, to hexadecyl phenyl, to 2-ethylhexyl phenyl, to 3, 7-dimethyl octyl phenyl and to 2-hexyl decyl phenyl, particularly preferably to dodecylphenyl, to pentadecylphenyl, to 2-ethylhexyl phenyl and to 3, 7-dimethyl octyl phenyl.
Ar 1the aromatic heterocycle of 3 shown valencys refers to from having substituent aromatic heterocyclic compounds remaining atomic group after 3 hydrogen atoms eliminating on aromatic nucleus.The carbonatoms that the aromatic heterocycle of 3 valencys has is generally 2 ~ 60, and preferably 4 ~ 60, more preferably 4 ~ 20.
As the substituting group that the heterogeneous ring compound with aromatic series can have, the group of such as halogen atom and 1 valency can be enumerated.Definition and the concrete example of the group of the definition of the group of 1 valency and 1 valency shown in concrete example with R are identical.
As the aromatic heterocycle of 3 valencys, the such as group shown in formula (201) ~ formula (301) can be enumerated.
(in formula, R represents implication same as described above.)
Ar 1the aromatic carbon ring base of 3 shown valencys refers to from having substituent aromatic hydrocarbon remaining atomic group after 3 hydrogen atoms eliminating on aromatic nucleus.The carbonatoms that the aromatic carbon ring base of 3 valencys has is generally 6 ~ 60, is preferably 6 ~ 20.
Aromatic hydrocarbon also comprise compound containing phenyl ring, the compound containing condensed ring, containing Direct Bonding more than 2 independently the structure of phenyl ring or condensed ring compound, more than 2 independently phenyl ring or condensed ring across the compound of the group bondings such as vinylidene.
As the substituting group that aromatic hydrocarbon can have, the group of such as halogen atom and 1 valency can be enumerated.Definition and the concrete example of the group of the definition of the group of 1 valency and 1 valency shown in concrete example with R are identical.
As the aromatic carbon ring base of 3 valencys, the such as group shown in formula (302) ~ formula (311) can be enumerated.
(in formula, R represents implication same as described above.)
In group shown in formula (201) ~ formula (311), from the view point of the monomer easily becoming the raw material of macromolecular compound of the present invention, preferred formula (202), formula (205), formula (206), formula (207), formula (210), formula (212), formula (220), formula (235), formula (238), formula (270), formula (271), formula (272), formula (273), formula (274), formula (275), formula (286), formula (287), formula (288), formula (291), formula (292), formula (293), formula (296), formula (301) and the group shown in formula (302), more preferably formula (235), formula (271), formula (272), formula (273), formula (274), formula (286), formula (291), formula (296), formula (301) and the group shown in formula (302), further preferred formula (271), formula (272), formula (273), formula (274) and the group shown in formula (311), the particularly preferably group shown in formula (273).
Ar 2the aromatic heterocycle of 4 shown valencys refers to from having substituently have the hetero ring type compound of aromatic series remaining atomic group after 4 hydrogen atoms removed on aromatic nucleus.The carbonatoms that the aromatic heterocycle of 4 valencys has is generally 2 ~ 60, is preferably 4 ~ 60, is more preferably 4 ~ 20.
As the substituting group that the hetero ring type compound with aromatic series can have, the group of such as halogen atom and 1 valency can be enumerated.Definition and the concrete example of the group of the definition of the group of 1 valency and 1 valency shown in concrete example with R are identical.
As the aromatic heterocycle of 4 valencys, the such as group shown in formula (401) ~ formula (447) can be enumerated.
(in formula, R represents implication same as described above.)
Ar 2the aromatic carbon ring base of 4 shown valencys refers to the remaining atomic group from having substituent aromatic hydrocarbon after 4 hydrogen atoms removing on aromatic nucleus.The carbonatoms that the aromatic carbon ring base of 4 valencys has is generally 6 ~ 60, is preferably 6 ~ 20.
As the substituting group that aromatic hydrocarbon can have, the group as halogen atom and 1 valency can be enumerated.Definition and the concrete example of the group of the definition of the group of 1 valency and 1 valency shown in concrete example with R are identical.
As the aromatic carbon ring base of 4 valencys, the such as group shown in formula (448) ~ formula (454) can be enumerated.
(in formula, R represents implication same as described above)
In group shown in formula (401) ~ formula (454), from the view point of the photoelectric transformation efficiency of the organic thin film solar cell improved containing macromolecular compound of the present invention, preferred formula (401), formula (402), formula (404), formula (405), formula (406), formula (411), formula (412), formula (430), formula (431), formula (432), formula (433), formula (444), formula (445), formula (446), formula (447), formula (448) and the group shown in formula (454), more preferably formula (411), formula (430), formula (431), formula (432), formula (444), formula (445), formula (447) and the group shown in formula (448), further preferably (411), formula (432), formula (444), formula (447) and the group shown in formula (448), particularly preferably formula (444) and the group shown in formula (448).
As the structural unit shown in formula (1) ~ (4), the such as structural unit shown in formula (501) ~ formula (646) can be enumerated.
(in formula, R represents implication same as described above.)
In structural unit shown in above-mentioned formula (501) ~ formula (646), from the view point of the easness of monomer of raw material becoming macromolecular compound of the present invention, preferred formula (501), formula (502), formula (517), formula (518), formula (529), formula (530), formula (533), formula (534), formula (537), formula (538), formula (553), formula (572), formula (574), formula (575), formula (590), formula (591), formula (602), formula (603), formula (606), formula (607), formula (610), formula (611), formula (626) and the structural unit shown in formula (645), more preferably formula (501), formula (517), formula (529), formula (537), formula (553), formula (572), formula (574), formula (590), formula (602), formula (610), formula (626) and the structural unit shown in formula (645), further preferred formula (501), formula (517), formula (529), formula (537), formula (553), formula (590), formula (602) and the structural unit shown in formula (610), particularly preferably formula (501) and the structural unit shown in formula (529).
Formula (1), (2), (3) or the structural unit shown in (4), from the view point of the photoelectric transformation efficiency of the organic photoelectric converter improved containing macromolecular compound of the present invention, preferred formula (5), formula (6), formula (7) or the structural unit shown in formula (8), more preferably formula (9), formula (10), formula (11) or the structural unit shown in formula (12).
In formula (5) ~ (8), X represent sulphur atom, Sauerstoffatom, selenium atom ,-NH-or-N (R)-.From the view point of the photoelectric transformation efficiency of the organic photoelectric converter improved containing macromolecular compound of the present invention, preferred sulphur atom.
Y represents nitrogen-atoms or=CH-.From the view point of the photoelectric transformation efficiency of the organic photoelectric converter improved containing macromolecular compound of the present invention, preferably=CH-.
Macromolecular compound of the present invention preferably except containing except the structural unit shown in formula (1) ~ (4), also contains the structural unit different from the structural unit shown in formula (1) ~ (4).When macromolecular compound of the present invention contains the structural unit different from the structural unit shown in formula (1) ~ (4), the structural unit shown in preferred formula (1) ~ (4) and the structural unit different from the structural unit shown in formula (1) ~ (4) form conjugation.Conjugation of the present invention refers to and clips a singly-bound between unsaturated link(age), presents interaction.At this, unsaturated link(age) refers to double bond or triple bond.
As the structural unit different from the structural unit shown in formula (1) ~ (4), the arylidene different from the structural unit shown in formula (1) ~ (4) or the heterocyclic radical of divalent can be enumerated.
This arylidene refers to the atomic group from having substituent aromatic hydrocarbon after 2 hydrogen atoms eliminating on aromatic nucleus, and the carbonatoms of this arylidene is generally 6 ~ 60, is preferably 6 ~ 20.Alternatively base, can enumerate the group of such as halogen atom and 1 valency.Definition and the concrete example of the group of the definition of the group of 1 valency and 1 valency shown in concrete example with R are identical.
As the structural unit different from the structural unit shown in formula (1) ~ (4), from the view point of the photoelectric transformation efficiency of the organic thin film solar cell improved containing macromolecular compound of the present invention, be preferably the structural unit shown in formula (Cy-1) ~ formula (Cy-5).
(in formula (Cy-1) ~ (Cy-5), R represents implication same as described above.R 1and R 2separately represent the group of hydrogen atom, halogen atom or 1 valency.R 1with R 2can link and form ring texture.Ring Cy represents identical or different, can have substituent aromatic nucleus.R 3represent the group of divalent.)
R 1and R 2definition and the concrete example of the group of the definition of the group of 1 shown valency and 1 valency shown in concrete example with R are identical.
R 1and R 2formation ring texture can be linked.The concrete example of ring texture is the structure shown in formula (D-1) ~ formula (D-5).
(in formula (D-1) ~ formula (D-5), R represents implication same as described above.)
Aromatic nucleus shown in ring Cy can be monocycle, also can be condensed ring.As the aromatic nucleus of monocycle, such as phenyl ring, pyrrole ring, furan nucleus, thiphene ring, oxazole ring, thiazole ring, Thiadiazole, pyrazole ring, pyridine ring, pyrazine ring, imidazole ring, triazole ring, isoxazole ring, isothiazole ring, pyrimidine ring, pyridazine ring and triazine ring can be enumerated.
As the aromatic nucleus of condensed ring, can enumerate and condense the aromatic nucleus of any ring on above-mentioned monocycle.As the ring condensed on monocycle, such as furan nucleus can be enumerated, thiphene ring, pyrrole ring, pyrroline ring, pyrrolidine ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, Thiadiazole, imidazole ring, tetrahydroglyoxaline ring, imidazolidine ring, pyrazole ring, pyrazoline ring, pyrazolidine ring, furazan ring, triazole ring, Thiadiazole, oxadiazole rings, tetrazole ring, pyranoid ring, pyridine ring, piperidine ring, thiapyran ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperazine ring, morpholine ring, triazine ring, cumarone ring, isobenzofuran ring, thionaphthene ring, indole ring, isoindole ring, indolizine ring, indoline ring, isoindoline ring, chromene ring, chroman ring, heterochromatic full ring, chromene ring, quinoline ring, isoquinoline 99.9 ring, quinolizine ring, benzoglyoxaline ring, benzothiazole ring, indazole ring, naphthyridines ring, quinoxaline ring, quinazoline ring, quinoline oxazolidine ring, cinnolines ring, phthalazines ring, purine skeleton, pteridine ring, carbazole ring, xanthene ring, phenanthridines ring, acridine ring, β-carboline ring, perimidine ring, phenanthroline ring, thianthrene ring, phenoxathiin ring, phenoxazine ring, thiodiphenylamine ring and azophenlyene ring.
In ring Cy, the substituting group that aromatic nucleus can have is the group of such as halogen atom and 1 valency.Definition and the concrete example of the group of the definition of the group of 1 valency and 1 valency shown in concrete example with R are identical.
R 3the concrete example of shown divalent group is the group shown in formula (b-1) ~ formula (b-5).
(in formula (b-1) ~ formula (b-5), R represents implication same as described above.)
As the structural unit shown in formula (Cy-1) ~ formula (Cy-5), the such as structural unit shown in formula (C-1) ~ formula (C-29) can be enumerated.
(in formula (C-1) ~ formula (C-29), R represents implication same as described above)
As the structural unit shown in formula (C-15), the structural unit shown in preferred formula (C-30) and the structural unit shown in formula (C-31).
Macromolecular compound of the present invention refers to that weight-average molecular weight is the compound of 1, more than 000.The weight-average molecular weight of macromolecular compound of the present invention is preferably 3, and 000 ~ 10,000,000.Weight-average molecular weight than 3,000 low time, when making element may there is defect in the film that formed, than 10,000,000 large time, may decline to the solvability of solvent or coating when making element.The weight-average molecular weight of macromolecular compound more preferably 4,000 ~ 5,000,000, is particularly preferably 5,000 ~ 1,000,000.
Weight-average molecular weight of the present invention refers to and uses gel permeation chromatography (GPC), the weight-average molecular weight of the polystyrene conversion using the Standard testing agent of polystyrene to calculate.
Formula (1), (2), (3) or the structural unit shown in (4), at least containing a kind in macromolecular compound of the present invention.Preferably each macromolecular chain is on average containing more than 2, and more preferably each macromolecular chain is on average containing more than 3.
When using macromolecular compound of the present invention in the component, from the view point of easily making element, preferred macromolecular compound solubleness is in a solvent high.Specifically, macromolecular compound of the present invention preferably has the solvability of the solution of this macromolecular compound that can make containing 0.01 weight (wt) more than %, more preferably there is the solvability of the solution that can make containing more than 0.1wt%, preferably there is the solvability of the solution that can make containing more than 0.2wt% further.
The manufacture method of macromolecular compound of the present invention, there is no particular limitation, from the view point of the easness of synthetic macromolecular compound, preferably uses the method for Suzuki linked reaction, Stille linked reaction.
As the method using Suzuki linked reaction, such as, can enumerate the manufacture method comprising following operation:
That is, by formula (100):
Q 100-E 1-Q 200(100)
(in formula, E 1structural unit shown in expression (Cy-1) ~ (Cy-5).Q 100and Q 200represent identical or different, dihydroxyl boryl (-B (OH) 2) or boric acid ester residue.〕
The compound of shown more than a kind and formula (200):
T 1-E 2-T 2(200)
(in formula, E 2structural unit shown in expression (1) ~ (4).T 1and T 2represent identical or different halogen atom.〕
The operation that the compound of shown more than a kind reacts under the existence of palladium catalyst and alkali.As E 1, the structural unit shown in preferred formula (C-1) ~ formula (C-29).
When compound shown in compound shown in formula (100) and formula (200) is reacted, the total of the mole number of the compound of more than a kind shown in formula (200) preferably used in the reaction, relative to the compound of more than a kind shown in formula (100) mole number add up to surplus.The mole number of the compound of more than a kind shown in formula (200) that uses in assumed response add up to 1 mole time, the total of the mole number of the compound of more than a kind shown in formula (100) is preferably 0.6 ~ 0.99 mole, is more preferably 0.7 ~ 0.95 mole.
Boric acid ester residue represents eliminate the group after hydroxyl from boric acid diester, as its concrete example, can enumerate the group shown in following formula.
(in formula, Me represents methyl, and Et represents ethyl.)
T in formula (200) 1and T 2shown halogen atom is fluorine atom, chlorine atom, bromine atoms or atomic iodine, from the easness of synthetic macromolecular compound, and preferred bromine atoms and atomic iodine, more preferably bromine atoms.
Specifically, as the method for carrying out Suzuki linked reaction, can enumerate and use palladium catalyst as catalyzer in arbitrary solvent, carry out the method for reacting in the presence of base.
As the palladium catalyst used in Suzuki linked reaction, such as Pd (O) catalyzer, Pd (II) catalyzer can be enumerated, specifically, preferably [four (triphenylphosphine)] palladium, acid chloride class, two (triphenylphosphine) palladium of dichloro, acid chloride, three (dibenzalacetone) two palladium, two (dibenzalacetone) palladium, from the view point of reaction (polymerization) easness, reaction (polymerization) speed that operate, preferred dichloro pair (triphenylphosphine) palladium, acid chloride, three (dibenzalacetone) two palladium.
There is no particular limitation for the addition of palladium catalyst, as long as the effective dose of catalyzer, usually relative to the compound 1 mole shown in formula (100), be 0.0001 mole ~ 0.5 mole, is preferably 0.0003 mole ~ 0.1 mole.
As the palladium catalyst used in Suzuki linked reaction, when using acid chloride class, the phosphorus compounds such as triphenylphosphine, three (o-tolyl) phosphine, three (o-methoxyphenyl) phosphine can be added as ligand.Now, the addition of ligand, relative to palladium catalyst 1 mole, is generally 0.5 mole ~ 100 moles, is preferably 0.9 mole ~ 20 moles, more preferably 1 mole ~ 10 moles.
As the alkali being used in Suzuki linked reaction, mineral alkali, organic bases, inorganic salt etc. can be enumerated.As mineral alkali, such as salt of wormwood, sodium carbonate, hydrated barta, potassiumphosphate can be enumerated.As organic bases, such as triethylamine, tributylamine can be enumerated.As inorganic salt, such as cesium fluoride can be enumerated.
As the addition of alkali, relative to the compound 1 mole shown in formula (100), be generally 0.5 mole ~ 100 moles, be preferably 0.9 mole ~ 20 moles, more preferably 1 mole ~ 10 moles.
Suzuki linked reaction is carried out usually in a solvent.As solvent, DMF, toluene, glycol dimethyl ether, tetrahydrofuran (THF), methylene dichloride can be illustrated.The deliquescent viewpoint of the macromolecular compound used from the present invention, preferred toluene, tetrahydrofuran (THF).In addition, as the interpolation of alkali, the aqueous solution containing alkali can be added in reaction solution, react with 2 phase systems of aqueous phase and organic phase.As alkali, when using inorganic salt, from the deliquescent viewpoint of inorganic salt, usually the aqueous solution containing alkali is added in reaction solution and make it reaction.
Be explained, when making it reaction with 2 phase systems, also can add the phase-transfer catalysts such as quaternary ammonium salt as required.
The temperature of carrying out Suzuki linked reaction is determined according to described solvent, but is generally 40 ~ 160 DEG C.Quantize from the view point of the polymer of macromolecular compound, preferably 60 ~ 120 DEG C.In addition, reflux near the boiling point that also can be warming up to solvent.Reaction times with the point of the polymerization degree that achieves the goal for terminal, can be generally 0.1 hour ~ 200 hours.0.5 hour ~ 30 hours are effective, thus preferably.
Suzuki linked reaction is carried out in the reaction system not making palladium catalyst inactivation in the torpescence such as argon gas, nitrogen atmosphere.Carry out in system such as after utilizing argon gas or nitrogen etc. fully degassed.Specifically, after it is degassed in nitrogen abundant metathesis polymerizable container (reaction system), the compound shown in formula (100) is added in this aggregation container, compound shown in formula (200), two (triphenylphosphine) palladium (II) of palladium catalyst such as dichloro, and then aggregation container nitrogen is fully replaced, after degassed, add carry out bubbling with nitrogen in advance thus degassed after solvent such as toluene after, drip in this solution carry out bubbling with nitrogen in advance thus degassed after alkali such as aqueous sodium carbonate after, heating, heat up, under such as reflux temperature, torpescence atmosphere is kept to be polymerized 8 hours.
As the method using Stille linked reaction, the manufacture method comprising following operation can be enumerated:
That is, by formula (300):
Q 300-E 3-Q 400(300)
(in formula, E 3structural unit shown in expression (Cy-1) ~ (Cy-5).Q 300and Q 400represent identical or different, replace stannyl.〕
The compound of shown more than a kind and the compound of more than a kind shown in described formula (200) react under the existence of palladium catalyst.As E 3, the structural unit shown in preferred formula (C-1) ~ formula (C-29).
Alternatively stannyl, can enumerate-SnR 100 3shown group etc.At this, R 100represent the organic group of 1 valency.As the organic group of 1 valency, such as alkyl and aryl can be enumerated.
As alkyl, the chain-like alkyls such as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, isopentyl, 2-methyl butyl, 1-methyl butyl, hexyl, isohexyl, 3-methyl amyl, 2-methyl amyl, 1-methyl amyl, heptyl, octyl group, iso-octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl can be enumerated; The cycloalkyl such as cyclopentyl, cyclohexyl, adamantyl.As aryl, phenyl, naphthyl etc. can be enumerated.Alternatively stannyl, preferably-SnMe 3,-SnEt 3,-SnBu 3and-SnPh 3, more preferably-SnMe 3,-SnEt 3and-SnBu 3.In above-mentioned preferred example, Me represents methyl, and Et represents ethyl, and Bu represents butyl, and Ph represents phenyl.
Specifically, as catalyzer, can enumerate such as under palladium catalyst, the method for reacting in arbitrary solvent.
As the palladium catalyst used in Stille linked reaction, such as Pd (0) catalyzer, Pd (II) catalyzer can be enumerated.Specifically, [four (triphenylphosphine)] palladium, acid chloride class, two (triphenylphosphine) palladium of dichloro, acid chloride, three (dibenzalacetone) two palladium, two (dibenzalacetone) palladium can be enumerated, from the view point of reaction (polymerization) easness, reaction (polymerization) speed that operate, preferred [four (triphenylphosphine)] palladium, three (dibenzalacetone) two palladium.
The addition of the palladium catalyst used in Stille linked reaction, there is no particular limitation, as long as effectively measure as catalyzer, but relative to the compound 1 mole shown in formula (100), be generally 0.0001 mole ~ 0.5 mole, be preferably 0.0003 mole ~ 0.2 mole.
In Stille linked reaction, ligand, promotor can be used as required.As ligand, the phosphorus compounds such as such as triphenylphosphine, three (o-tolyl) phosphine, three (o-methoxyphenyl) phosphine, three (2-furyl) phosphine can be enumerated; The arsenic compounds such as triphenylarsine, triple phenoxyl arsine.As promotor, cupric iodide, cupric bromide, cupric chloride, 2-thiophenic acid copper (I) etc. can be enumerated.
When using ligand or promotor, the addition of ligand or promotor, relative to palladium catalyst 1 mole, is generally 0.5 mole ~ 100 moles, is preferably 0.9 mole ~ 20 moles, more preferably 1 mole ~ 10 moles.
Stille linked reaction is carried out usually in a solvent.As solvent, DMF, N, N-N,N-DIMETHYLACETAMIDE, toluene, glycol dimethyl ether, tetrahydrofuran (THF) etc. can be enumerated.The deliquescent viewpoint of the macromolecular compound used from the present invention, preferred toluene, tetrahydrofuran (THF).
The temperature of carrying out Stille linked reaction is determined according to above-mentioned solvent, but is generally 50 ~ 160 DEG C, quantizes from the view point of the polymer of macromolecular compound, is preferably 60 ~ 120 DEG C.In addition, carry out refluxing near the boiling point being warming up to solvent.
Carry out the time (reaction times) of described reaction, with some when reaching targeted degree of polymerization for terminal, but be generally 0.1 hour ~ 200 hours.1 hour ~ 30 hours are effective, thus preferably.
Stille linked reaction, under the torpescence such as argon gas, nitrogen atmosphere, is carried out in the reaction system of Pd catalyzer non-inactivation.Carry out in system such as after argon gas, nitrogen etc. are fully degassed.Specifically, fully replace in aggregation container (reaction system) with nitrogen, after degassed, the compound shown in formula (300), compound, the palladium catalyst shown in formula (200) is added in this aggregation container, and then aggregation container nitrogen is fully replaced, degassed after, add carry out bubbling with nitrogen in advance thus degassed after solvent such as toluene after, add ligand, promotor as required, then heat, heat up, under such as reflux temperature, keep torpescence atmosphere to be polymerized 8 hours.
The number-average molecular weight of the polystyrene conversion of macromolecular compound is preferably 1 × 10 3~ 1 × 10 8.The number-average molecular weight of polystyrene conversion is 1 × 10 3time above, easily obtain tough film.On the other hand, 10 8time following, solvability is high, makes film easy.
When the terminal group of macromolecular compound of the present invention directly remains polymerization activity base, characteristic, the life-span of the element obtained when the making being used in element may reduce, and therefore can protect with stable group.Preferably having the structure with the conjugated structure continuous print conjugated link(age) of main chain, in addition, also can be the structure across such as vinylidene and aryl or heterocyclic radical bonding.
There is the macromolecular compound of the present invention of formula (1), (2), (3) or the structural unit shown in (4), synthesized as one of raw material such as formula the compound shown in the compound shown in (13) or formula (14) by example.
In formula (13) and formula (14), R represents implication same as described above.4 R can be identical or different respectively.
W represents hydrogen atom, halogen atom, boric acid ester residue, dihydroxyl boryl, formyl radical, vinyl or replaces stannyl, and 2 W can be identical or different.
When using the compound shown in formula (13) that W is hydrogen atom, manufacture the macromolecular compound with the structural unit shown in formula (I) by oxypolymerization.In oxypolymerization, usually catalyzer can be used.As described catalyzer, known catalyzer can be used.Such as can use the mixture (metal halide/amine complex) of metal halide, metal halide and amine complex.As metal halide, the halogenide of 1 valency of the metals such as copper, iron, vanadium, chromium, divalent or 3 valencys can be used.
As the amine used in the manufacture of amine complex, such as pyridine, lutidine, glyoxal ethyline, N, N, N can be enumerated ', N '-Tetramethyl Ethylene Diamine.Metal halide/amine complex is by a solvent, mixed metal halide and amine manufacture in the presence of oxygen, the molar ratio that metal halide is mixed with amine, as being metal halide/amine=1/0.1 ~ 1/200, is preferably 1/0.3 ~ 1/100.
As catalyzer, iron(ic) chloride (Polym.Prep.Japan, Vol.48,309 (1999)) can be used.And then, by using copper/amine catalyst system (J.Org.Chem., 64,2264 (1999), J.Polym.Sci.PartA, Polym.Chem., 37,3702 (1999)), the molecular weight of macromolecular compound can be improved.
As the solvent in oxypolymerization, as long as the solvent of poisoning of catalyst can not be made, can be not particularly limited to use.As described solvent, such as hydrocarbon solvent, ether solvents, alcoholic solvent can be enumerated.At this, as hydrocarbon solvent, such as toluene, benzene, dimethylbenzene, Three methyl Benzene, tetramethyl-benzene, naphthalene, tetraline can be enumerated.As ether solvents, such as Anaesthetie Ether, Di Iso Propyl Ether, tetrahydrofuran (THF), Isosorbide-5-Nitrae-diox, diphenyl ether, t-butyl methyl ether can be enumerated.As alcoholic solvent, such as methyl alcohol, ethanol, Virahol, 2-methyl cellosolve can be enumerated.
The temperature of reaction of oxypolymerization is generally-100 DEG C ~ 100 DEG C, is preferably-50 ~ 50 DEG C.
When macromolecular compound of the present invention is multipolymer, as the method manufacturing multipolymer, the method that two or more monomer of mixing carries out being polymerized can be enumerated, the method etc. of the 2nd kind of monomer will be added after a kind of monomer polymerization.By using above-mentioned method, or combinationally using above-mentioned method, segmented copolymer, random copolymers, alternating copolymer, segmented copolymer, graft copolymer etc. can be manufactured.
Easily change from the view point of functional group, preferably same or different, halogen atom, boric acid ester residue, the dihydroxyl boryl and replace stannyl of the W in formula (13) and formula (14).
When W in compound shown in formula (13) is hydrogen atom, as the method W in the compound shown in formula (13) being converted to bromine atoms, known method can be used, the compound shown in formula (13) such as making W be hydrogen atom can be enumerated and contact the method for carrying out bromination with bromine or N-bromosuccinimide (NBS).The condition of bromination can at random set, but due to the bromination rate of the method for such as reacting with NBS in a solvent high, and the selectivity of the importing position of bromine atoms is high, thus preferably.As the solvent now used, DMF, chloroform, methylene dichloride, tetracol phenixin etc. can be enumerated.Reaction times is generally 1 minute ~ 10 hours, and temperature of reaction is generally-50 DEG C ~ about 50 DEG C.The amount of the bromine used relative to the W compound 1 mole shown in formula (13) that is hydrogen atom, is preferably 1 mole ~ about 5 moles.After reaction, such as add after water makes reaction stop and using organic solvent extraction product, distillation, except common aftertreatments such as desolventizings, can obtain the compound shown in formula (13) that W is bromine atoms.The separation of product and refining by carrying out based on methods such as chromatographic separation and Extraction or recrystallizations.
It is long wavelength that macromolecular compound preferred light of the present invention absorbs end wavelength.Photoabsorption end wavelength is tried to achieve by following method.
Be used in ultraviolet, spectrophotometer (such as Japanese light splitting system, UV, visible light near infrared spectrometer JASCO-V670) that visible, near infrared wavelength region may can work measures.When using JASCO-V670, the wavelength region that can measure is 200 ~ 1500nm, therefore measures in this wavelength region.First, the absorption spectrum of the substrate used in mensuration is measured.As substrate, use quartz base plate, glass substrate etc.Then, the film containing macromolecular compound is formed by the solution containing macromolecular compound or the molten mass containing macromolecular compound on the substrate.When being filmed based on solution, after masking, carry out drying.Then, the absorption spectrum of the duplexer of film and substrate is obtained.Using the absorption spectrum of the difference between the absorption spectrum of the duplexer of film and substrate and the absorption spectrum of substrate as film.
In the absorption spectrum of this film, the longitudinal axis represents the absorbancy of macromolecular compound, and transverse axis represents wavelength.Preferably the absorbancy of its maximum absorption band is made to be about 0.5 ~ 2 to the thickness adjustment of film.In absorption peak, suppose that the absorbancy of the absorption peak that wavelength is the longest is 100%, by containing 50% the straight line parallel with transverse axis (wavelength axis) of absorbancy and the peak-to-peak intersection point of this absorption and the longer intersection point of the wavelength of peak this absorption peak of wavelength ratio is set to the first point.By containing 25% the straight line parallel with wavelength axis of absorbancy and the intersection point of this absorption peak and the longer intersection point of the wavelength of peak this absorption peak of wavelength ratio is set to the 2nd point.Link the 1st and the straight line of the 2nd and the intersection point of reference line are defined as photoabsorption end wavelength.At this, reference line refers in the absorption peak that wavelength is the longest, the absorbancy setting this absorption peak is 100%, setting contains the straight line parallel with wavelength axis of absorbancy and the intersection point of this absorption peak of 10%, and the wavelength of the longer intersection point of the wavelength of peak this absorption peak of wavelength ratio is as benchmark, using wavelength ratio as the 3rd point on the absorption spectrum of the long 100nm of wavelength of benchmark, with wavelength ratio as the 4th straight line linked on the absorption spectrum of the long 150nm of wavelength of benchmark.
Macromolecular compound of the present invention can play high electron-transporting properties and/or cavity conveying, therefore by when being used for element containing the organic film of this macromolecular compound, can carry from the electronics of electrode injection, hole or the electric charge that produced by photoabsorption.Above-mentioned characteristic is made full use of, can be used in the various electronic components such as photo-electric conversion element, OTFT, organic electroluminescent device.Below, these elements are described respectively.
Photo-electric conversion element containing macromolecular compound of the present invention, has the active coating of more than 1 layer containing macromolecular compound of the present invention between the pair of electrodes that at least one party is transparent or semitransparent.
As the preferred implementation of the photo-electric conversion element containing macromolecular compound of the present invention, have: the active coating that at least one party is transparent or semitransparent pair of electrodes and is formed by p-type organic semiconductor and N-shaped organic semi-conductor organic composite.Macromolecular compound of the present invention is preferably used as p-type organic semiconductor.
The photo-electric conversion element of macromolecular compound manufacture of the present invention is used usually to be formed on substrate.As long as this substrate formed electrode, form organic layer time there is not chemical transformation.As the material of substrate, such as glass, plastics, polymeric membrane, silicon can be enumerated.When opaque substrate, preferably to electrode, the electrode namely away from substrate is transparent or semitransparent.
Other embodiments with the photo-electric conversion element of macromolecular compound of the present invention are following photo-electric conversion element: between the pair of electrodes that at least one party is transparent or semitransparent containing containing macromolecular compound of the present invention the 1st active coating and adjoin with the 1st active coating and the 2nd active coating containing the electron acceptor compound such as fullerene derivate.
As transparent or semitransparent electrode materials, the metal oxide film of electroconductibility, translucent metallic film etc. can be enumerated.Specifically, the conductive material comprising Indium sesquioxide, zinc oxide, stannic oxide and their mixture and indium tin oxide (ITO), indium-zinc oxide etc. can be used; NESA, gold, platinum, silver, copper, preferred ITO, indium-zinc oxide, stannic oxide.As the making method of electrode, vacuum vapour deposition, sputtering method, ion plating method, plating etc. can be enumerated.
As electrode materials, organic nesa coatings such as Polyaniline and its derivative, Polythiophene and derivative thereof can be used.
The electrode of one side may not be transparent.As the electrode materials of this electrode, metal, electroconductive polymer etc. can be used.As the concrete example of electrode materials, can enumerate more than a kind in alloy of more than two kinds in the metals such as lithium, sodium, potassium, rubidium, caesium, magnesium, calcium, strontium, barium, aluminium, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium and these metals or above-mentioned metal with the alloy of the metal of more than a kind in gold and silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten and tin, graphite, compound between graphite layers, Polyaniline and its derivative, Polythiophene and derivative thereof.As the example of alloy, magnesium-silver alloys, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloys, lithium-aluminium alloy, lithium-magnesium alloy, lithium-indium alloy, calcium-aluminium alloy etc. can be enumerated.
As the method for improving photoelectric transformation efficiency, the additional middle layer beyond active coating can be used.As the material being used as middle layer, the oxide compound such as halogenide, titanium oxide, PEDOT (poly-3,4-rthylene dioxythiophene) etc. of the basic metal such as lithium fluoride, alkaline-earth metal can be enumerated.
Active coating can contain a kind of macromolecular compound of the present invention separately, also capable of being combined containing two or more.In order to improve the cavity conveying of active coating, as electron donating property compound and/or electron acceptor compound, can compound in active coating beyond macromolecular compound of the present invention used in combination.Be explained, electron donating property compound, electron acceptor compound relatively can be determined according to the rank of the energy level of these compounds.
As electron donating property compound, except macromolecular compound of the present invention, such as pyrazoline derivative can also be enumerated, arylamine derivatives, stilbene derivative, triphenyl diamine derivative, oligothiophene and derivative thereof, polyvinyl carbazole and derivative thereof, polysilane and derivative thereof, side chain or main chain have the polyorganosiloxane ramification of aromatic amine residue, Polyaniline and its derivative, Polythiophene and derivative thereof, polypyrrole and derivative thereof, poly-aryl ethane (polyarylene vinylene) and derivative thereof, and polythiophenevinylenand (polythienylene vinylene) and derivative etc. thereof.
As electron acceptor compound, except macromolecular compound of the present invention, such as carbon material can be adopted, the metal oxides such as titanium oxide, oxadiazole derivative, anthraquinone bismethane (anthraquinodimethane) and derivative thereof, benzoquinones and derivative thereof, naphthoquinones and derivative thereof, anthraquinone and derivative thereof, four cyano anthraquinone bismethane and derivative thereof, fluorenone derivatives, phenylbenzene dicyanoethylene and derivative thereof, diphenoquinone, the metal complex of oxine and derivative thereof, poly quinoline and derivative thereof, polyquinoxaline and derivative thereof, polyfluorene and derivative thereof, 2, 9-dimethyl-4, 7-phenylbenzene-1, 10-phenanthroline (bathocuproine, phenanthroline derivative, soccerballene, the fullerene derivate such as bathocuproine).Preferential oxidation titanium, carbon nanotube, soccerballene, fullerene derivate, particularly preferably soccerballene, fullerene derivate.
As soccerballene, fullerene derivate, C can be enumerated 60, C 70, C 76, C 78, C 84and derivative.Fullerene derivate represent soccerballene at least partially by the compound modified.
As fullerene derivate, the such as compound shown in formula (15), the compound shown in formula (16), the compound shown in formula (17), the compound shown in formula (18) can be enumerated.
(in formula (15) ~ (18), R afor commutable alkyl, aryl, aromatic heterocycle or the group with ester structure.Multiple R acan be identical or different.R brepresent commutable alkyl or aryl.Multiple R bcan be identical or different.)
R aand R bdefinition and the concrete example of shown commutable alkyl and the definition of aryl and the commutable alkyl shown in concrete example with R and aryl are identical.
As R ashown aromatic heterocycle, can enumerate such as thienyl, pyrryl, furyl, pyridyl, quinolyl and isoquinolyl.
R athe shown group with ester structure can enumerate the such as group shown in formula (19).
(in formula, u1 represents the integer of 1 ~ 6, and u2 represents the integer of 0 ~ 6, R crepresent commutable alkyl, aryl or aromatic heterocycle.)
R cthe definition of shown commutable alkyl, aryl and aromatic heterocycle and concrete example and R adefinition and the concrete example of shown commutable alkyl, aryl and aromatic heterocycle are identical.
As C 60the concrete example of the derivative of soccerballene, can enumerate following compound.
As C 70the concrete example of the derivative of soccerballene, can enumerate following compound.
In addition, as the example of fullerene derivate, can [6 be enumerated, 6] phenyl-C61 methyl-butyrate (C60PCBM, [6, 6]-Phenyl C61 butyric acid methyl ester), [6, 6] phenyl-C71 methyl-butyrate (C70PCBM, [6, 6]-Phenyl C71 butyric acid methyl ester), [6, 6] phenyl-C85 methyl-butyrate (C84PCBM, [6, 6]-Phenyl C85butyric acid methylester), [6, 6] thienyl-C61 methyl-butyrate ([6, 6]-Thienyl C61butyric acid methylester).
Time in active coating containing macromolecular compound of the present invention and fullerene derivate, the amount of fullerene derivate, relative to macromolecular compound 100 weight part of the present invention, is preferably 10 ~ 1000 weight parts, is more preferably 20 ~ 500 weight parts.
The thickness of active coating is preferably 1nm ~ 100 μm usually, is more preferably 2nm ~ 1000nm, more preferably 5nm ~ 500nm, is more preferably 20nm ~ 200nm.
The manufacture method of described active coating manufactures by arbitrary method, can enumerate and such as carry out the method for film forming based on the solution containing macromolecular compound, carry out the method for film forming based on vacuum vapour deposition.
The preferable production process of photo-electric conversion element is the manufacture method having the 1st electrode and the 2nd electrode and have the element of active coating between the 1st electrode and the 2nd electrode, it is included in the operation that the solution (black liquid) that the 1st electrode contains macromolecular compound of the present invention and solvent by coating method coating forms active coating, and on this active coating, form the operation of the 2nd electrode.
As the solvent of use when carrying out film forming based on solution, as long as macromolecular compound of the present invention can be made to dissolve.As this solvent, the unsaturated hydrocarbons kind solvents such as such as toluene, dimethylbenzene, sym-trimethylbenzene, tetraline, perhydronaphthalene, bicyclohexyl, butylbenzene, sec-butylbenzene, tert.-butylbenzene can be enumerated; The halo saturated hydrocarbons solvents such as tetracol phenixin, chloroform, methylene dichloride, ethylene dichloride, chlorobutane, n-butyl bromide, chloropentane, bromo pentane silane, chlorohexane, bromohexane, chlorine hexanaphthene, bromine hexanaphthene; The halo unsaturated hydrocarbons kind solvents such as chlorobenzene, dichlorobenzene, trichlorobenzene; The ether solvent such as tetrahydrofuran (THF), tetrahydropyrans.Macromolecular compound of the present invention dissolves more than 0.1 % by weight usually in these solvents.
When using solution to carry out film forming, slot coated method can be adopted, scraper for coating method, method of spin coating, casting method, micro-gravure coating process, gravure coating process, stick coating method, rolling method, coiling rod coating method (wirebar coating), Dipcoat method, spraying method, silk screen print method, woodburytype, flexographic printing process (flexo printing), flexographic printing process (offset printing), ink-jet application method, divider print process (dispenser printing), the coating processes such as nozzle coating method and kapillary coating method (capillary coating), preferred employing slot coated method, kapillary coating method, gravure coating process, micro-gravure coating process, stick coating method, scraper for coating method, nozzle coating method, ink-jet application method and method of spin coating.
From the view point of film-forming properties, the surface tension of the solvent of 25 DEG C is preferably greater than 15mN/m, be less than 100mN/m more preferably greater than 15mN/m, is less than 60mN/m more preferably greater than 25mN/m.
Macromolecular compound of the present invention also can be used for OTFT.As OTFT, can enumerate and possess source electrode and drain electrode, the organic semiconductor layer (active coating) becoming the current path between these electrodes and the OTFT controlled by the structure of the gate electrode of the magnitude of current of this current path.Organic semiconductor layer is made up of above-mentioned organic film.As this type of OTFT, field effect type, electrostatic induction etc. can be enumerated.
Field effect type OTFT preferably has source electrode and drain electrode, become the organic semiconductor layer (active coating) of the current path between these electrodes, control by the gate electrode of the magnitude of current of this current path and the insulation layer that is configured between organic semiconductor layer and gate electrode.Particularly preferably source electrode and drain electrode connect with organic semiconductor layer (active coating) and arrange, and then preferably clamp the insulation layer that contacts with organic semiconductor layer and arrange gate electrode.In field effect type OTFT, organic semiconductor layer is made up of the organic film containing macromolecular compound of the present invention.
Electrostatic induction OTFT preferably has source electrode and drain electrode, the organic semiconductor layer (active coating) becoming the current path between them and the gate electrode controlled by the magnitude of current of current path, and this gate electrode is arranged in organic semiconductor layer.Particularly preferably source electrode, drain electrode and the gate electrode that is arranged in organic semiconductor layer connect with organic semiconductor layer and arrange.At this, as the structure of gate electrode, as long as form current path from source electrode to drain electrode that flow from and the voltage putting on gate electrode can be utilized to carry out the structure of the magnitude of current in control flow check overcurrent path, such as, comb poles can be enumerated.In electrostatic induction OTFT, organic semiconductor layer is made up of the organic film containing macromolecular compound of the present invention.
Macromolecular compound of the present invention also can be used in organic electroluminescent device (organic EL).In organic EL, between the pair of electrodes that at least one party is transparent or semitransparent, there is luminescent layer.Organic EL, except containing except luminescent layer, also can contain hole transporting layer, electron supplying layer.Containing macromolecular compound of the present invention in the random layer of this luminescent layer, hole transporting layer, electron supplying layer.Except containing except macromolecular compound of the present invention in luminescent layer, also charge transport material (general name of electron transport materials and hole transporting material) can be contained.As organic EL, the element with anode, luminescent layer and negative electrode can be enumerated; And then enumerate the element between negative electrode and luminescent layer with the anode, luminescent layer, electron supplying layer and the negative electrode that to adjoin with this luminescent layer and there is the electron supplying layer containing electron transport materials; And then the element between anode and luminescent layer with the anode, hole transporting layer, luminescent layer and the negative electrode that to adjoin with this luminescent layer and there is the hole transporting layer containing hole transporting material can be enumerated; There is the element etc. of anode, hole transporting layer, luminescent layer, electron supplying layer and negative electrode.
Using the photo-electric conversion element of macromolecular compound of the present invention by irradiating the light such as sunlight from transparent or translucent electrode, photoelectromotive force can be produced between electrode, make it as organic thin film solar cell work.By by integrated for organic thin film solar cell multiple, can also use as organic thin film solar cell module.
In addition, by under the state that is applied with voltage between to electrode, or without under the state applied, from transparent or translucent electrode incident light, will photoelectric current be flow through, can make it to work as organic optical sensor.By by integrated for organic optical sensor multiple, can also use as organic image sensor.
Above-mentioned OTFT can be used as such as the control of the pixel of electrophoretic display device (EPD), liquid-crystal display, display of organic electroluminescence etc., the image-driven element etc. of the control of image brightness uniformity, image switching speed.
Organic thin film solar cell can take the modular structure substantially identical with solar module in the past.In general solar module takes following structure: Component units on the supporting substrates such as metal, pottery; by on it with the covering such as potting resin or protective glass; from the opposite side lead-in light of supporting substrates; also following structure can be adopted: supporting substrates uses the transparent material such as chilled glass, thereon Component units and from this transparent supporting substrates side lead-in light.Specifically, there will be a known and be referred to as substrate-integrated modular structure etc. used in the modular structure, amorphous si solar cells etc. of super straight type, sub-straight type (sub straight type), embedding type.Also according to application target or field of employment and environment, these modular structures can suitably be selected applying in the organic thin film solar cell that macromolecular compound of the present invention manufactures.
The module of representational super straight type or sub-straight type is following structure: the transparent and arrangement unit at certain intervals between the supporting substrates being implemented antireflection process in one or both sides, by the connection such as metal lead wire or flexible distribution between adjacent unit, be configured with collecting electrodes in outer edge, produced electric power is externally derived.Between substrate and unit, in order to protected location or raising current collecting efficiency, also the various plastic materials such as ethylene vinyl acetate (EVA) can be used according to object with the form of film or potting resin.In addition; when the place etc. that the impact from outside is few does not need the place covered by the hard material in surface to use; also can form sealer with transparent plastic film, or defencive function can be given by making above-mentioned potting resin solidify, thus cancel the substrate of side.In order to ensure the sealing of inside and the rigidity of module, the metal framework of the surrounding of supporting substrates is fixed with sandwich-like, sealing material sealing blocking will be used between supporting substrates and framework.In addition, if use the material of flexibility in unit itself or supporting substrates, packing material and sealing material, then also solar cell can be formed on curved surface.When employing the solar cell of the flexible support such as polymeric film, can by sending the supporting mass of drum while forming unit successively, after being cut into required size, by circumference, the flexible and material seal with moisture resistance is to make battery main body.In addition, Solar Energy Materials and Solar Cells can also be adopted, the modular structure being referred to as " SCAF " recorded in 48, p383-391.In addition, the solar cell employing flexible support also can be adhesively fixed on the upper uses such as bend glass.
Embodiment
Below, in order to illustrate in greater detail the present invention exemplified with embodiment, but the present invention is not limited thereto.
(NMR mensuration)
NMR measures by making compound dissolution in deuterochloroform, uses NMR device (Varian Inc., INOVA300) to carry out.
(mensuration of number-average molecular weight and weight-average molecular weight)
The number-average molecular weight that p-poly-phenyl ethene converts and weight-average molecular weight, obtained by gel permeation chromatography (GPC, Shimadzu Seisakusho Ltd.'s system, trade(brand)name: LC-10Avp).The macromolecular compound measured is dissolved in tetrahydrofuran (THF) the concentration reaching about 0.5 % by weight, injects GPC 30 μ L.The moving phase of GPC uses tetrahydrofuran (THF), flows through with the flow velocity of 0.6mL/ minute.Post uses TSKgelSuperHM-H (eastern Cao's system) 2 and TSKgel SuperH2000 (eastern Cao's system) 1 to be connected in series.Detector uses differential refraction rate detector (Shimadzu Seisakusho Ltd.'s system, trade(brand)name: RID-10A).
Synthesis example 1 (synthesis of compound 2)
In four-hole boiling flask, add 11.84g (40.00mmol) compound 1, two (tetramethyl ethylene ketone conjunction) two boron 25.39g (100.0mmol), (100.0mmol) is Ji diox 200mL for Potassium ethanoate 9.814g, in the reaction solution obtained, under room temperature (25 DEG C), import argon gas 30 minutes, carry out bubbling.Add diphenylphosphino ferrocene dichloro palladium 1.633g (2.000mmol), diphenylphosphino ferrocene 1.109g (2.000mmol) in reaction solution after, reflux 20 hours.After reflux, liquid phase chromatography is utilized to confirm the disappearance of raw material.By reaction solution by diatomite filtration, after insoluble component separating, make filtrate drying except desolventizing, obtain brown solid.The brown solid obtained is dissolved in the hot methanol of 200mL, carries out recrystallization, obtain 6.11g compound 2 thus.
1H-NMR(CDCl 3，δ(ppm))：1.354(s，24H)，3.821(s，6H)，7.153(s，2H)
Synthesis example 2 (synthesis of compound 4)
In four-hole boiling flask, add 5.00g (24.1mmol) compound 3, methyl alcohol 100mL and vitriol oil 1mL, under reflux conditions react 10 hours.After reaction, confirmed the disappearance of raw material by liquid phase chromatography.Then, in reaction solution, add water and chloroform, extract organic layer.After distillation removing chloroform, the silica gel column chromatography that the crude product obtained employs hexane by developing solvent is refined, obtains 5.08g compound 4.
1H-NMR(CDCl 3，δ(ppm))：3.883(s，3H)，7.224(d，1H)，7.362(d，1H)
Synthesis example 3 (synthesis of compound 5)
In four-hole boiling flask, add 2.11g (10.00mmol) compound 4 and 100mL tetrahydrofuran (THF), in the reaction solution obtained, under room temperature (25 DEG C), import argon gas carry out bubbling in 30 minutes.Then, in reaction solution, add the aqueous potassium phosphate solution 15.0g (30.0mmol) of three (dibenzalacetone) palladium 45.8mg (0.05mmol), [three (tertiary butyl) phosphorus] Tetrafluoroboric acid ester 58.0mg (0.20mmol) and 2mol/L.While reaction solution is stirred at 80 DEG C, dripped with 5 minutes and 1.95g compound 2 (5.00mmol) is dissolved in the solution formed in the tetrahydrofuran (THF) of 20mL.After 2 hours, confirmed the disappearance of raw material by liquid phase chromatography.Then, in reaction solution, add water and chloroform, extract organic layer.After distillation removing chloroform, the column chromatography that the crude product obtained employs chloroform by developing solvent is refined, obtains 1.76g compound 5.
1H-NMR(CDCl 3，δ(ppm))：3.738(s，12H)，6.932(s，2H)，7.301(d，2H)，7.501(d，2H)
Synthesis example 4 (synthesis of compound 6)
In four-hole boiling flask, add 628mg (1.50mmol) compound 5 and tetrahydrofuran (THF) 40mL, in the reaction solution obtained, under room temperature (25 DEG C), import argon gas carry out bubbling in 30 minutes.Reaction solution is cooled to 0 DEG C, adds the tetrahydrofuran solution 24mL of the pentadecyl bromination magnesium containing 0.5mol/L, stir 30 minutes.Reaction solution is warming up to 40 DEG C, stirs 6 hours.Then, in reaction solution, add water and chloroform, extract organic layer.After distillation removing chloroform, the column chromatography that the crude product obtained employs chloroform by developing solvent is refined, obtains brown powder.Brown powder utilized following mixing solutions to wash, obtain 884mg compound 6, described mixing solutions is that methyl alcohol and ethanol mix relative to the mode that the volumetric ratio of the volume of methyl alcohol is 1 with the volume of ethanol.
Synthesis example 5 (synthesis of compound 7)
In four-hole boiling flask, add 880mg (0.731mmol) compound 6 and 20mL methylene dichloride, in the reaction solution obtained, under room temperature (25 DEG C), import argon gas 30 minutes, carry out bubbling.In reaction solution, add the dichloromethane solution 2.92mL of the boron tribromide containing 1mol/L, at room temperature stir 3 hours.Then, in reaction solution, add water and chloroform, extract organic layer.Then, distillation removing chloroform, obtains the brown oil 800mg containing compound 7.
Embodiment 1 (synthesis of compound 8)
In eggplant type flask, add brown oil 800mg, toluene 20mL and the tosic acid 2mg of the compound 7 comprising synthesis in synthesis example 5, stir 5 hours at 60 DEG C.Then, in reaction solution, add water and chloroform, extract organic layer.After distillation removing chloroform, the column chromatography that the crude product obtained employs hexane by developing solvent is refined, obtains 92.3mg compound 8.
1H-NMR(CDCl 3，δ(ppm))：0.874(t，12H)，1.244(m，104H)，1.843(m，8H)，
6.734(d，2H)，6.818(s，2H)，7.150(d，2H)
Embodiment 2 (synthesis of compound 9)
In four-hole boiling flask, add 92.3mg (0.081mmol) compound 8, tetrahydrofuran (THF) 30mL, in the reaction solution obtained, under room temperature (25 DEG C), import 30 minutes argon gas, carry out bubbling.After reaction solution being cooled to 0 DEG C, add 31.7mg (0.178mmol) NBS, be warming up to room temperature (25 DEG C).After 5 hours, confirmed the disappearance of raw material by liquid phase chromatography.Then, in reaction solution, add sodium thiosulfate solution, and then add hexane, carry out the extraction of organic layer.Then, employ the isolated composition of chromatographic column of hexane from utilizing developing solvent and remove desolventizing, carry out drying, obtain 94.1mg compound 9.
1H-NMR(CDCl 3，δ(ppm))：0.876(t，12H)，1.223(m，52H)，1.248(m，52H)，
1.789(m，8H)，6.647(s，1H)，6.695(s，1H)
Synthesis example 6 (synthesis of compound 11)
In four-hole boiling flask, add 16.31g (100.0mmol) compound 10, Anaesthetie Ether 326mL, in the reaction solution obtained, under room temperature (25 DEG C), import argon gas 30 minutes, carry out bubbling.After reaction solution is cooled to-78 DEG C, add the tetrahydrofuran solution 40.4mL containing 2.6mol/L butyllithium (n-BuLi), stir 1 hour.Then, add two (pentadecyl) ketone 47.3g (105.0mmol), after being warming up to room temperature, stir 2 hours.Then, in reaction solution, add aqueous acetic acid, and then add the extraction that hexane carries out organic layer.Add hot ethanol in the brown solid obtained after distillation removing hexane, extract target compound, obtain 49.2g compound 11.
1H-NMR(CDCl 3，δ(ppm))：0.879(t，6H)，1.253(m，52H)，1.746(m，4H)，
6.960(d，1H)，7.266(d，1H)
Synthesis example 7 (synthesis of compound 12)
In eggplant type flask, add 17.8g (33.3mmol) compound 11, ethanol 150mL and vitriol oil 2mL, stir 2 hours at 50 DEG C, confirmed the disappearance of raw material by liquid phase chromatography.Then, in reaction solution, add water and chloroform, extract organic layer.After distillation removing chloroform, the column chromatography that the crude product obtained employs hexane by developing solvent is refined, obtains 13.8g compound 12.
1H-NMR(CDCl 3，δ(ppm))：0.884(t，6H)，1.130(t，3H)，1.235(m，52H)，
1.774(m，4H)，3.150(q，2H)，7.051(m，2H)，7.242(d，1H)
Synthesis example 8 (synthesis of compound 13)
In four-hole boiling flask, add 5.63g (10.0mmol) compound 12, Anaesthetie Ether 100mL, in the reaction solution obtained, under room temperature (25 DEG C), import 30 minutes argon gas, carry out bubbling.After reaction solution is cooled to-50 DEG C, add the tetrahydrofuran solution 4.0ml containing 2.6mol/L butyllithium (n-BuLi), stir 1 hour.Then, add 2-isopropoxy-4,4,5,5-tetramethyl--1,3,2-dioxa boron penta ring 1.95g (10.50mmol), after being warming up to room temperature, stir 2 hours.Then, in reaction solution, add water, and then add hexane, carry out the extraction of organic layer.Use hot methanol to clean the brown oil obtained after hexane distillation removing, obtain 6.48g compound 13.
1H-NMR(CDCl 3，δ(ppm))：0.879(t，6H)，1.204(t，3H)，1.252(m，52H)，
1.335(s，12H)，1.989(m，4H)，3.224(q，2H)，
7.264(d，1H)，7.422(d，1H)
Synthesis example 9 (synthesis of compound 15)
In four-hole boiling flask, add 5.00g (20.74mmol) compound 14, triethylamine 150mL and methylene dichloride 500mL, in the reaction solution obtained, at 40 DEG C, import 30 minutes argon gas, carry out bubbling.In reaction solution after sulfur oxychloride 5.00g (42.03mmol), reflux 1 hour.After reflux, confirmed the disappearance of raw material by liquid phase chromatography.Then, the solvent in distillation removing reaction solution, in the solid obtained, add water, stirring and washing 30 minutes, filtered water obtains coarse crystallization.Use methyl alcohol to carry out the recrystallization of coarse crystallization, obtain 3.30g compound 15.
1H-NMR(CDCl 3，δ(ppm))：4.024(s，6H)，7.202(s，2H)
Synthesis example 10 (synthesis of compound 16)
In four-hole boiling flask, add 3.30g (16.82mmol) compound 15, acetic acid 20mL and chloroform 100mL, in the reaction solution obtained, under room temperature (25 DEG C), import 30 minutes argon gas, carry out bubbling.Then, in reaction solution, add bromine 3.5mL (67.97mmol), at room temperature react 24 hours.After reaction, confirmed the disappearance of raw material by liquid phase chromatography.Then, in reaction solution, adding sodium thiosulfate solution, by carrying out the extraction operation using chloroform, obtaining coarse crystallization.Use the column chromatography of following mixing solutions to obtain coarse crystallization by developing solvent, described mixing solutions is mixing solutions hexane and chloroform mixed relative to the mode that the volumetric ratio of the volume of hexane is 1 with the volume of chloroform.Then, carry out the recrystallization using methyl alcohol, obtain 4.44g compound 16.
1H-NMR(CDCl 3，δ(ppm))：4.051(s，6H)
Synthesis example 11 (synthesis of compound 17)
In four-hole boiling flask, add 354mg (1.00mmol) compound 16 and tetrahydrofuran (THF) 10mL, in the reaction solution obtained, under room temperature (25 DEG C), import argon gas 30 minutes, carry out bubbling.Then, in reaction solution, add the aqueous potassium phosphate solution 2.5g of three (dibenzalacetone) palladium 36.6mg (0.04mmol), [three (tertiary butyl) phosphorus] Tetrafluoroboric acid ester 46.4mg (0.16mmol) and 2mol/L.Add the solution be dissolved in by 1.38g compound 13 (2.00mmol) in 5mL tetrahydrofuran (THF) while being stirred at 80 DEG C by reaction solution, stir.After 2 hours, confirmed the disappearance of raw material by liquid phase chromatography.Then, in reaction solution, add water and hexane, extract organic layer.After hexane distillation is removed, the column chromatography that the crude product obtained employs following mixed solvent by developping agent is refined, obtain 687mg compound 17, described mixed solvent is that hexane and chloroform mix relative to the mode that the volumetric ratio of the volume of chloroform is 4 with the volume of hexane.
1H-NMR(CDCl 3，δ(ppm))：0.731(t，6H)，0.884(t，12H)，1.250(m，96H)，
1.750(m，8H)，3.120(m，8H)，3.843(s，6H)，
7.154(d，2H)，7.386(d，2H)
Synthesis example 12 (synthesis of compound 18)
In four-hole boiling flask, add 279mg (0.211mmol) compound 17 and methylene dichloride 40mL, in the reaction solution obtained, under room temperature (25 DEG C), import argon gas 30 minutes, carry out bubbling.In reaction solution, add the dichloromethane solution 1.27mL (1.27mmol) containing 1mol/L boron tribromide, at room temperature stir 2 hours.Then, in reaction solution, add aqueous acetic acid and chloroform, extract organic layer.By the chloroform distillation removing in organic layer, obtain the brown oil 300mg containing compound 18.
Embodiment 3 (synthesis of compound 19)
In eggplant type flask, add brown oil 300mg, the toluene 10mL containing the compound 18 of synthesis in synthesis example 12 and tosic acid 1mg, stir 10 hours at 60 DEG C.Then, in reaction solution, add water and chloroform, extract organic layer.After chloroform distillation removing, use the column chromatography of hexane to refine by developing solvent the crude product obtained, obtain 52.1mg compound 19.
1H-NMR(CDCl 3，δ(ppm))：0.872(t，12H)，1.208(m，48H)，1.241(m，48H)，
1.414(m，8H)，1.973(m，8H)，
6.826(d，2H)，7.375(d，2H)
Embodiment 4 (synthesis of compound 20)
In four-hole boiling flask, add 52.1mg (0.043mmol) compound 19, tetrahydrofuran (THF) 20mL, in the reaction solution obtained, under room temperature (25 DEG C), import argon gas 30 minutes, carry out bubbling.After reaction solution being cooled to 0 DEG C, add 16.8mg (0.095mmol) NBS, be warming up to room temperature (25 DEG C).After 3 hours, confirmed the disappearance of raw material by liquid phase chromatography.Then, in reaction solution, add sodium thiosulfate solution, and then add hexane, carry out the extraction of organic layer.Then, use the chromatographic column of hexane to carry out the separation of organic layer by developing solvent, the composition that separation is obtained carries out drying except desolventizing, obtains 57.8mg compound 20.
1H-NMR(CDCl 3，δ(ppm))：0.872(t，12H)，1.213(m，48H)，1.241(m，48H)，1.417(m，8H)，1.955(m，8H)，6.775(s，2H)
Synthesis example 13 (synthesis of compound 22)
In 500ml flask, add fluoro-1, the 2-diaminobenzene of 4,5-bis-(compound 21) (Tokyo changes into industry system) 10.2g (70.8mmol), pyridine 150mL, make homogeneous solution.Flask is cooled to 0 DEG C, in flask, drips sulfur oxychloride 16.0g (134mmol).After dropping, flask is heated to 25 DEG C, carries out reaction in 6 hours.Then, in reaction solution, add water 250ml, and then add chloroform, extract the organic layer containing reaction product.Chloroformic solution and organic layers with sodium sulfate are carried out drying, concentrates with vaporizer, the solid of precipitation is refined by recrystallization.The solvent of recrystallization uses methyl alcohol.After refining, obtain 10.5g (61.0mmol) compound 22.
1H-NMR(CDCl 3，δ(ppm))：7.75(s，2H)
19F-NMR(CDCl 3，δ(ppm))：-128.3(s，2F)
Synthesis example 14 (synthesis of compound 23)
In 100mL flask, add 2.00g (11.6mmol) compound 22, iron powder 0.20g (3.58mmol), flask is heated to 90 DEG C.Bromine 31g (194mmol) was dripped with 1 hour in this flask.After dropping, reaction solution is stirred 38 hours at 90 DEG C.Then, flask is cooled to room temperature (25 DEG C), adds chloroform 100mL and dilute.The solution obtained is injected the sodium sulfite aqueous solution 300mL of 5wt%, stir 1 hour.The organic layer of the mixed solution that separation and Extraction obtains, by water layer chloroform extraction 3 times.The extracting solution obtained is mixed in organic layer, mixed solution sodium sulfate is carried out drying, with vaporizer distillation except desolventizing concentrates.The yellow solid obtained is dissolved to and is heated to, in the methyl alcohol 90mL of 55 DEG C, then be cooled to 25 DEG C.The crystallization of precipitation filtered, obtain crystallization, then, drying under reduced pressure under room temperature (25 DEG C), obtains 1.50g compound 23.
19F-NMR(CDCl 3，δ(ppm))：-118.9(s，2F)
Synthesis example 15 (synthesis of compound 24)
In four-hole boiling flask, add 12.30g (37.28mmol) compound 23, two (tetramethyl ethylene ketone conjunction) two boron 23.67g (93.20mmol), (93.20mmol) is Ji diox 500mL for Potassium ethanoate 9.15g, in the reaction solution obtained, under room temperature (25 DEG C), import argon gas with 30 minutes, carry out bubbling.Add diphenylphosphino ferrocene dichloro palladium 1.52g (1.86mmol), diphenylphosphino ferrocene 1.03mg (1.86mmol) in reaction solution after, reflux 60 hours.After backflow, confirmed the disappearance of raw material by liquid phase chromatography.Reaction solution diatomite is filtered, after insoluble component separating, makes filtrate drying except desolventizing, obtain brown solid.In the brown solid obtained, add hot hexane 200mL filter, make filtrate drying except desolventizing, obtain coarse crystallization.Then, with hexane, coarse crystallization is carried out recrystallization.Carry out 2 recrystallizations, obtain 3.12g compound 24.
1H-NMR(CDCl 3，δ(ppm))：1.45(s，24H)
19F-NMR(CDCl 3，δ(ppm))：-117(s，2F)
Embodiment 5 (synthesis of polymer A)
In four-hole boiling flask, add 45.4mg (0.035mmol) compound 9 and tetrahydrofuran (THF) 5mL, in the reaction solution obtained, under room temperature (25 DEG C), import argon gas 30 minutes, carry out bubbling.Then, in reaction solution, add the aqueous potassium phosphate solution 0.2g (0.4mmol) of three (dibenzalacetone) palladium 0.64mg (0.0007mmol), [three (tertiary butyl) phosphorus] Tetrafluoroboric acid ester 0.81mg (0.0028mmol), 2mol/L.Reaction solution is stirred under the temperature of oil bath is the condition of 80 DEG C, the compound 25 (0.035mmol) of 13.6mg is dissolved in the tetrahydrofuran (THF) of 2mL simultaneously, the solution obtained was dripped with 10 minutes, stirs 30 minutes.Then, in reaction solution, add phenyl-boron dihydroxide 3.5mg (0.029mmol), and then stir after 1 hour, stopped reaction.Be explained, react and carry out in argon gas atmosphere.
Then, in reaction solution, add Thiocarb 1.0g and pure water 9.0mL, reflux and stir while 3 hours.After water layer in removing reaction solution, organic layers with water 10ml is cleaned 2 times, cleans 2 times with the aqueous acetic acid 10mL of 3 weight (wt) %, and then clean 2 times with water 10mL, inject methyl alcohol and polymkeric substance is separated out.By dry after polymer filtration, by the polymer dissolution that obtains in toluene.By toluene solution by aluminum oxide/silicagel column, the solution obtained is injected methyl alcohol polymkeric substance is separated out.By making it dry after polymer filtration, obtain 25mg polymer A.
The molecular weight (polystyrene conversion) of the polymer A that GPC measures, counts 96,000 with weight-average molecular weight (Mw), counts 32,000 with number-average molecular weight (Mn).The absorption limit wavelength of polymer A is 780nm.
Embodiment 6 (synthesis of polymer B)
In four-hole boiling flask, add 48.7mg (0.038mmol) compound 9 and methylene dichloride 5.3mL, in the reaction solution obtained, under room temperature (25 DEG C), import 30 minutes argon gas, carry out bubbling.Then, in reaction solution, add the aqueous potassium phosphate solution 0.2g (0.4mmol) of three (dibenzalacetone) palladium 1.37mg (0.0015mmol), [three (tertiary butyl) phosphorus] Tetrafluoroboric acid ester 1.74mg (0.006mmol), 2mol/L.Reaction solution is stirred under the temperature of oil bath is the condition of 40 DEG C, makes the compound 24 (0.038mmol) of 15.9mg be dissolved in the methylene dichloride of 2.3mL, the solution obtained thus was dripped with 10 minutes, stirs 30 minutes.Then, in reaction solution, add phenyl-boron dihydroxide 3.8mg (0.031mmol), and then stir after 1 hour, stopped reaction.Be explained, react and carry out in argon gas atmosphere.
Then, add Thiocarb 1.0g and pure water 9.0mL to reaction solution, reflux and stir for 3 hours.After water layer in removing reaction solution, organic layers with water 10ml is cleaned 2 times, cleans 2 times with the aqueous acetic acid 10mL of 3 weight (wt) %, and then clean 2 times with water 10mL, inject in methyl alcohol and polymkeric substance is separated out.It will be made after polymer filtration dry, by the polymer dissolution that obtains in toluene.Toluene solution is passed into aluminum oxide/silicagel column, the solution obtained is injected methyl alcohol polymkeric substance is separated out.By making it dry after polymer filtration, obtain 13mg polymer B.
For the molecular weight (polystyrene conversion) of the polymer B measured with GPC, count 35,000 with weight-average molecular weight (Mw), count 16,000 with number-average molecular weight (Mn).The absorption limit wavelength of polymer B is 770nm.
Embodiment 7 (synthesis of polymkeric substance C)
In four-hole boiling flask, add 57.6mg (0.043mmol) compound 20 and tetrahydrofuran (THF) 3mL, in the reaction solution obtained, under room temperature (25 DEG C), import 30 minutes argon gas, carry out bubbling.Then, in reaction solution, add the aqueous potassium phosphate solution 0.2g (0.4mmol) of three (dibenzalacetone) palladium 1.95mg (0.0021mmol), [three (tertiary butyl) phosphorus] Tetrafluoroboric acid ester 2.47mg (0.0085mmol), 2mol/L.Reaction solution is stirred under the temperature of oil bath is the condition of 80 DEG C, dripped with 10 minutes and the compound 25 (ALDRICH Inc.) (0.043mmol) of 16.5mg is dissolved in the solution obtained in the tetrahydrofuran (THF) of 2mL, stir 30 minutes.Then, in reaction solution, add phenyl-boron dihydroxide 4.3mg (0.029mmol), and then stir after 1 hour, stopped reaction.Be explained, reaction is carried out in argon gas atmosphere.
Then, in reaction solution, add Thiocarb 1.0g and pure water 9.0mL, reflux and stir for 3 hours simultaneously.After the water layer removing in reaction solution, organic layers with water 10ml is cleaned 2 times, cleans 2 times with the aqueous acetic acid 10mL of 3 weight (wt) %, and then clean 2 times with water 10mL, inject methyl alcohol and polymkeric substance is separated out.It will be made after polymer filtration dry, by the polymer dissolution that obtains in toluene.Toluene solution is passed in aluminum oxide/silicagel column, the solution obtained is injected methyl alcohol polymkeric substance is separated out.By making it dry after polymer filtration, obtain 37mg polymkeric substance C.
For the molecular weight (polystyrene conversion) of the polymkeric substance C measured with GPC, count 167,000 with weight-average molecular weight (Mw), count 51,000 with number-average molecular weight (Mn).The absorption limit wavelength of polymkeric substance C is 820nm.
Embodiment 8 (synthesis of polymkeric substance D)
In four-hole boiling flask, add 54.2mg (0.040mmol) compound 20 and methylene dichloride 2.8mL, in the reaction solution obtained, under room temperature (25 DEG C), import 30 minutes argon gas, carry out bubbling.Then, in reaction solution, add the aqueous potassium phosphate solution 0.2g (0.4mmol) of three (dibenzalacetone) palladium 1.83mg (0.002mmol), [three (tertiary butyl) phosphorus] Tetrafluoroboric acid ester 2.32mg (0.008mmol) and 2mol/L.Reaction solution is stirred under the temperature of oil bath is the condition of 40 DEG C, dripped with 10 minutes and the compound 24 (0.040mmol) of 17.0mg is dissolved in the solution obtained in the methylene dichloride of 1.2mL, stir 30 minutes.Then, in reaction solution, add phenyl-boron dihydroxide 4.0mg (0.033mmol), and then stir after 1 hour, stopped reaction.Be explained, reaction is carried out under an argon atmosphere.
Then, in reaction solution, add Thiocarb 1.0g and pure water 9.0mL, reflux and stir for 3 hours.After water layer in removing reaction solution, organic layers with water 10ml is cleaned 2 times, cleans 2 times with the aqueous acetic acid 10mL of 3 weight (wt) %, and then clean 2 times with water 10mL, inject methyl alcohol and polymkeric substance is separated out.It will be made after polymer filtration dry, by the polymer dissolution that obtains in toluene.Toluene solution is passed into in aluminum oxide/silicagel column, the solution obtained is injected methyl alcohol polymkeric substance is separated out.By making it dry after polymer filtration, obtain 20mg polymkeric substance D.
For the molecular weight (polystyrene conversion) of the polymkeric substance D measured with GPC, count 42,000 with weight-average molecular weight (Mw), count 20,000 with number-average molecular weight (Mn).The absorption limit wavelength of polymkeric substance D is 800nm.
Synthesis example 16 (synthesis of compound 27)
1.78g (10.0mmol) compound 26,2-ethylhexyl bromide 5.83g (25.0mmol), potassiumiodide 41.5mg (0.25mmol), potassium hydroxide 1.68g (30.0mmol) is added in the 200mL flask of the gas in the flask by argon replaces, be dissolved in dimethyl sulfoxide (DMSO) 35mL, stir 24 hours under room temperature (25 DEG C).After reaction, add water 100mL, use hexane extraction product, use the silicagel column of hexane to refine by developing solvent, obtain 2.61g compound 27.
Synthesis example 17 (synthesis of compound 28)
1.31g (3.25mmol) compound 27 and 25mLN is added, dinethylformamide (DMF) in the 200mL flask of the gas in the flask by argon replaces.Then, flask is cooled to 0 DEG C, adds N-bromosuccinimide (NBS) 1.21g, stir 12 hours.In reaction solution, add water 100mL, stopped reaction, extract product with ether.Use the silicagel column of hexane to refine product by developing solvent, obtain 1.70g compound 28.
Synthesis example 18 (synthesis of polymkeric substance E)
561mg (1.00mmol) compound 28, compound 25 (4 is added in the 200mL flask of the gas in the flask by argon replaces, 7-two (4,4,5,5-tetramethyl--1,3,2-dioxa boron penta ring-2-base)-2,1,3-diazosulfide) (SUGMA ALDRICH Inc.) 388.1mg (1.00mmol), adogen (trade(brand)name Aliquat336 (registered trademark), SUGMAALDRICH Inc.) 202mg, be dissolved in toluene 20ml.Argon gas is imported, bubbling 30 minutes in the toluene solution obtained.Then, in reaction solution, add the aqueous sodium carbonate 6.5mL of palladium 2.25mg, three (2-p-methoxy-phenyl) phosphine (Tris (2-methoxyphenyl) phosphine) 12.3mg, 16.7wt%, stir 5 hours at 100 DEG C.Then, in reaction solution, add phenyl-boron dihydroxide 50mg, and then react 2 hours at 70 DEG C.Then, in reaction solution, add Thiocarb 2g and water 20mL, reflux and stir for 2 hours.After water layer in removing reaction solution, organic layers with water 20ml is cleaned 2 times, cleans 2 times with the aqueous acetic acid 20mL of 3wt%, and then clean 2 times with water 20mL, inject methyl alcohol and polymkeric substance is separated out.Drying is carried out, by the polymer dissolution that obtains in orthodichlorobenzene 30mL by after polymer filtration.O-dichlorobenzene solution is passed in aluminum oxide/silicagel column, the solution obtained is injected methyl alcohol polymkeric substance is separated out.By making it dry after polymer filtration, obtain 280mg polymkeric substance E.For the molecular weight (polystyrene conversion) of the polymkeric substance E measured with GPC, count 30,000 with Mw, count 14 with Mn, 000.
Embodiment 9 (making of organic transistor)
By have thickness be the high-concentration dopant of the heat oxide film of 300nm n-type silicon substrate in acetone ultrasonic cleaning after 10 minutes, irradiate the ozone UV of 20 minutes.Then, β-styroyl (phenethyl) trichlorosilane is gathered with syringe, in toluene, drip β-phenylethyltrichlorosilane with the ratio that β-phenylethyltrichlorosilane is 5 relative to toluene 10ml, make the toluene solution of the β-phenylethyltrichlorosilane of dilution.This toluene solution is coated on heat oxide film by spin-coating method, silane treatment is carried out to the surface of heat oxide film.
Then, polymer A be dissolved in orthodichlorobenzene, the concentration of preparation polymer A is the solution of 0.5 % by weight, this solution film filter is carried out filtration and makes coating fluid.This coating fluid is coated on the substrate after above-mentioned surface treatment by spin-coating method, forms the coated film of polymer A.The thickness of this coated film is about 30nm.And then by the thermal treatment 30 minutes at 170 DEG C in nitrogen atmosphere of this coated film, form the organic semiconductor thin film of polymer A.
And then, by employing the vacuum vapour deposition of metal mask, organic semiconductor thin film making source electrode and the drain electrode from organic semiconductor thin film side with the stepped construction of molybdic oxide and gold, manufactures organic transistor thus.
Embodiment 10 (evaluation of organic transistor)
Semiconductor Parameter Analyzer 4200 (KEITHLEY Inc.) is used to measure the electrical characteristic of organic transistor.Consequently, leakage current (Id) is good relative to the change curve of drain voltage (Vd), and be applied to the negative gate voltage of gate electrode if increase, then negative leakage current also increases, and confirms that organic transistor is p-type organic transistor.The field effect mobility degree μ of the current carrier of organic transistor uses the following formula (a) of the leakage current Id of the zone of saturation of the electrical characteristic representing organic transistor to calculate.
Id=(W／2L)μCi(Vg-Vt) 2···(a)
(in formula, L represents that the passage of organic transistor is long, W represents the channel width of organic transistor, Ci represents the capacity of every cellar area of gate insulating film, Vg represents gate voltage, and Vt represents the threshold voltage of gate voltage.)
Consequently, the field effect mobility degree (carrier mobility degree) of current carrier is 7.5 × 10 -3cm 2/ Vs, ON/OFF current ratio is 10 5.Show the result in table 1.
Embodiment 11
Except using polymer B to replace except polymer A, making organic transistor element with method similarly to Example 9, using method evaluation transistor characteristic similarly to Example 10.Carrier mobility degree is 7.0 × 10 -4cm 2/ Vs, ON/OFF current ratio is 10 4.Show the result in table 1.
Embodiment 12
Except using polymkeric substance C to replace except polymer A, making organic transistor element by method similarly to Example 9, using method evaluation transistor characteristic similarly to Example 10.Carrier mobility degree is 2.1 × 10 -3cm 2/ Vs, ON/OFF current ratio is 10 5.Show the result in table 1.
Embodiment 13
Except using polymkeric substance D to replace except polymer A, making organic transistor element with method similarly to Example 9, using method evaluation transistor characteristic similarly to Example 10.Carrier mobility degree is 5.0 × 10 -4cm 2/ Vs, ON/OFF current ratio is 10 4.Show the result in table 1.
Table 1 organic transistor element evaluation result
Embodiment 14 (making of black liquid and organic thin film solar cell, evaluation)
The glass substrate that attached to ito film with the thickness of 150nm by sputtering method is carried out ozone UV process, carries out surface treatment thus.Then, by polymer A and Fullerene C20 PCBM (phenyl C61-methyl-butyrate) (phenyl C61-butyric acid methyl ester, F-CARBON Inc.), be dissolved in orthodichlorobenzene with C60PCBM relative to the mode that the weight ratio of polymer A is 3, manufacture black liquid.Relative to the weight of black liquid, the weight of polymer A and the weight of C60PCBM add up to 2.0 % by weight.This black liquid is coated on glass substrate by spin-coating method, makes the organic membrane containing polymer A.Thickness is about 100nm.The photoabsorption end wavelength of the organic membrane made thus is 780nm.Then, over an organic film by vacuum evaporation plating machine with thickness 2nm evaporation lithium fluoride, then, with thickness 100nm evaporating Al, manufacture organic thin film solar cell.The shape of the organic thin film solar cell obtained is the square of 2mm × 2mm.The organic thin film solar cell obtained is used solar simulator (light splitting gauge system, trade(brand)name OTENTO-SUNI I:AM1.5Gfilter, radioluminescence intensity 100mW/cm 2) irradiate certain light, measure the electric current and voltage that produce, obtain photoelectric transformation efficiency, short-circuit current density, open voltage, packing factor (fill factor).Jsc (short-circuit current density) is 2.64mA/cm 2, Voc (opening end voltage) for 0.81V, ff (fillfactor (packing factor)) be 0.55, photoelectric transformation efficiency (η) is 1.24%.Show the result in table 2.
Embodiment 15
Except using polymkeric substance C to replace except polymer A, make black liquid by method similarly to Example 14 and organic thin film solar cell is evaluated.Jsc (short-circuit current density) is 2.65mA/cm 2, Voc (opening end voltage) for 0.79V, ff (fill factor (packing factor)) be 0.59, photoelectric transformation efficiency (η) is 1.22%.Show the result in table 2.
Embodiment 16
Except using polymkeric substance D to replace except polymer A, make black liquid by method similarly to Example 14 and organic thin film solar cell is evaluated.Jsc (short-circuit current density) is 2.67mA/cm 2, Voc (opening end voltage) for 0.91V, ff (fill factor (packing factor)) be 0.64, photoelectric transformation efficiency (η) is 1.57%.Show the result in table 2
Comparative example 1
Except using polymkeric substance E to replace except polymer A, making black liquid and organic thin film solar cell by method similarly to Example 14, evaluating.Jsc (short-circuit current density) is 4.61mA/cm 2, Voc (opening end voltage) for 0.60V, ff (fill factor (packing factor)) be 0.33, photoelectric transformation efficiency (η) is 0.91%.Show the result in table 2.
Table 2 photo-electric conversion element evaluation result
Utilizability in industry
The opening end voltage with the organic thin film solar cell of the organic layer containing macromolecular compound of the present invention is large, thus useful.

Claims (11)

1. a macromolecular compound, structural unit shown in its contained (1), formula (2), formula (3) or the structural unit shown in formula (4) and formula (Cy-1) ~ formula (Cy-5), weight-average molecular weight is 5,000 ~ 1,000,000, and each macromolecular chain on average containing more than 3 formula (1), formula (2), formula (3) or the structural unit shown in formula (4)
In formula (1) ~ formula (4), Ar 1represent the aromatic carbon ring base of 3 valencys of carbonatoms 6 ~ 60 or the aromatic heterocycle of 3 valencys of carbonatoms 2 ~ 60, Ar 2represent the aromatic carbon ring base of 4 valencys of carbonatoms 6 ~ 60 or the aromatic heterocycle of 4 valencys of carbonatoms 2 ~ 60, Z represent-O-,-S-,-C (=O)-, R represents the group of hydrogen atom, halogen atom or 1 valency, 2 Ar 1can be identical or different, 2 Z can be identical or different, and multiple R can be identical or different respectively,
In formula (Cy-1) ~ (Cy-5), R represents implication same as described above, R 1and R 2separately represent the group of hydrogen atom, halogen atom or 1 valency, R 1with R 2can link and form ring texture, ring Cy represents identical or different, can have substituent aromatic nucleus, R 3represent the group of divalent.
2. macromolecular compound according to claim 1, wherein,
Formula (1), formula (2), formula (3) or the structural unit shown in formula (4) are formula (5), the structural unit shown in formula (6), formula (7) or formula (8),
In formula (5) ~ formula (8), X represent sulphur atom, Sauerstoffatom, selenium atom ,-NH-or-N (R)-, Ar 2, Z and R represent implication same as described above, Y represents nitrogen-atoms or=CH-, and 2 X can be identical or different, and 2 Y can be identical or different.
3. macromolecular compound according to claim 1, wherein,
Formula (1), formula (2), formula (3) or the structural unit shown in formula (4) are formula (9), the structural unit shown in formula (10), formula (11) or formula (12),
In formula (9) ~ formula (12), Ar 2and R represents implication same as described above.
4. the macromolecular compound according to any one of claims 1 to 3, wherein,
The number-average molecular weight of polystyrene conversion is more than 3000.
5. a film, it contains the macromolecular compound according to any one of Claims 1 to 4.
6. a composition, it contains macromolecular compound according to any one of Claims 1 to 4 and electron acceptor compound.
7. composition according to claim 6, wherein,
Described electron acceptor compound is fullerene derivate.
8. a film, it contains the composition described in claim 6 or 7.
9. an electronic component, it uses the film described in claim 5 or 8.
10. the compound shown in formula (13),
In formula, R represents the group of hydrogen atom, halogen atom or 1 valency, and W represents hydrogen atom, halogen atom, boric acid ester residue, dihydroxyl boryl, formyl radical, vinyl or replaces stannyl, and 4 R can be identical or different respectively, and 2 W can be identical or different.
Compound shown in 11. 1 kinds of formulas (14),
In formula, R represents the group of hydrogen atom, halogen atom or 1 valency, and W represents hydrogen atom, halogen atom, boric acid ester residue, dihydroxyl boryl, formyl radical, vinyl or replaces stannyl, and 4 R can be identical or different respectively, and 2 W can be identical or different.
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